MAKALAH ANALITIK LANJUT

“METODE ANALISIS TRANSMISSION ELECTRON MICROSCOPY

(TEM)”

DISUSUN OLEH :
AMELIA I.PANAWAR
17 501 005
ILMU KIMIA/SEM 6

UNIVERSITAS NEGERI MANADO

FAKULTAS MATEMATIKA DAN ILMU PENGERTAHUAN ALAM

JURUSAN KIMIA

TAHUN 2020
 BAB I

PENDAHULUAN

A. Latar Belakang
Perkembangan ilmu pengetahuan memberikan dampak yang positif terhadap
perkembangan teknologi. Kemajuan ilmu pengetahuan yang berorientasi pada
pengembangan teknologi dan informasi merupakan bagian dari kehidupan masyarakat
dunia saat ini khususnya kalangan akademisi, banyak cara yang dapat dilakukan untuk
memanfaatkan perkembangan teknologi saat ini dalam memperoleh informasi, salah
satunya adalah dalam mendeteksi struktur permukaan berbagai jenis sampel atau contoh
bahan yang dibutuhkan di dalam suatu penelitian.
Dewasa ini hampir semua bidang IPTEK, serta jaminan kualitas mutu produksi
dalam dunia industri, terutama industri berbasis teknologi tinggi tidak dapat lepas dari
pemantauan skala mikro (sepermiliar milimeter) atau bahkan pemantauan pada skala
yang jauh lebih kecil hingga beberapa puluh nanometer dengan menggunakan mikroskop.
Salah satu jenis mikroskop yang berkembang sekarang ini adalah mikroskop elektron
yang terdiri dari Transmission Electron Microscopy (TEM) dan Scanning Electron
Microscopy (SEM).
Scanning Electron Microscopy (SEM) menghasilkan bayangan dengan resolusi
yang tinggi, maksudnya adalah pada jarak yang sangat dekat tetap dapat menghasilkan
perbesaran yang maksimal tanpa memecahkan gambar. Transmission Electron
Microscopy (TEM) adalah sebuah mikroskopdimana sebuah berkas elektronditembakkan
melalui spesimen ultra tipis.
Seorang ilmuwan dari universitas Berlinyaitu Dr. Ernst Ruska menggabungkan
penemuan elektron dan membangun mikroskop transmisi elektron (TEM) yang pertama
pada tahun 1931. Untuk hasil karyanya ini maka dunia ilmu pengetahuan
menganugerahinya hadiah Penghargaan Nobeldalam fisika pada tahun 1986. Mikroskop
yang pertama kali diciptakannya adalah dengan menggunakan dua lensa medan magnet,
namun tiga tahun kemudian ia menyempurnakan karyanya tersebut dengan
menambahkan lensa ketiga dan mendemonstrasikan kinerjanya yang menghasilkan
 resolusi hingga 100 nanometer(nm), dua kali lebih baik dari mikroskop cahaya pada masa
itu (azis,nur oktavian:2009).

B. Tujuan
Untuk Mengetahui Metode Analisis Scanning Electron Microscopy Prinsip kerja dan
Bagian-bagian alat TEM.
 BAB II
PEMBAHASAN

1. Pengertian TEM

TEM adalah salah satu jenis mikroskop yang memanfaatkan adanya penemuan elektron.
Mikroskop ini memanfaatkan elektron dan mentransmisikannya sehingga ditangkap oleh
sebuah layar yang akan menghasilkan gambar dari struktur material tersebut. Secara
mudahnya cara kerja TEM sama dengan cara kerja dari sebuah slide proyektor.

Gambar 1. Menunjukkan bentuk dari TEM, dimana komponen-komponennya terdiri atas

12 bagian. Setiap bagian memiliki bentuk dan fungsi yang berbeda-beda.

2. Komponen Transmission Electron Microscopy (TEM)

Bagian-bagian dari TEM ditunjukkan pada gambar 2 :
Berikut ini adalah bagian-bagian dari TEM :
a. Virtual Source di bagian atas mewakili senapan elektron, yang berfungsi
menghasilkan elektron monokromatik.
b. Lensa kondensor yaitu aliran elektron difokuskan pada berkas yang kecil, tipis dan
koheren dengan menggunakan lensa kondensor 1 dan 2. Lensa 1 (biasanya
dikontrol oleh tombol "spot size”) sangat menentukan ukuran dari besarnya aliran
mengenai sampel. Lensa kedua (biasanya dikontrol tombol “intensitas/brightness”)
yang mengubah ukuran spot pada sampel.
c. Berkas dibatasi oleh aperture dari kondensor (biasanya dapat dipilih pengguna),
merobohkan sudut tinggi elektron (yang jauh dari sumbu optik, garis putus-putus
di tengah-tengah). Aperture Terdiri dari disc logam kecil yang cukup tebal untuk
mencegah elektron dari melewati disc, sementara mengijinkan aksial electron.
Fungsi apertures:
1) Mengurangi intensitas sinar elektron disaring dari balok, yang
mungkindiinginkan dalam kasus sampel berkas sensitif.
2) Penyaringan ini melepaskan elektron yang tersebar. d. Berkas elektron
menumbuk spesimen kemudian, bagian-bagiannya ditransmisikan.
e. Bagian yang ditransmisikan difokuskan oleh lensa objektif menjadi sebuah
gambar.
f. Tujuan dan pilihan opsional logam Area aperture dapat membatasi sinar. Objective
aperture meningkatkan kontras dengan menghalangi difraksi elektron yang high
angle, yang dipilih aperture memungkinkan penggunauntuk secara berkala
memeriksa difraksi elektron oleh atom dalam sampel.
g. Gambar selanjutnya terus melalui intermediate dan lensa proyektor, yang
diperbesar sepanjang jalan.
h. Gambar-gambar membentur layar fosfor dan cahaya yang dihasilkan
memungkinkan pemakai untuk melihat gambar. Daerah yang lebih gelap
mewakili wilayah yang elektronnya lebih sedikit sedangkan daerah yang lebih
terang mewakili electron yang lebih banyaki (mereka lebih tipis atau kurang
padat) (Oktaviana,Aptika:2009)
3. Cara Kerja Transmission Electron Microscopy (TEM)

Mikroskop elektron transmisi menggunakan berkas elektron energi tinggi ditularkan

melalui sampel yang sangat tipis untuk gambar dan menganalisis mikrostruktur bahan
dengan resolusi skala atom. Elektron difokuskan dengan lensa elektromagnetik dan
gambar diamati pada layar fluorescent atau direkam dalam film atau kamera digital.
Elektron dipercepat di beberapa ratus kV, memberikan panjang gelombang jauh lebih
kecil daripada cahaya: 200kV elektron memiliki panjang gelombang 0.025Å. Namun,
resolusi mikroskop optik dibatasi oleh panjang gelombang cahaya, yaitu mikroskop
elektron dibatasi oleh penyimpangan yang melekat pada lensa elektromagnetik, menjadi
sekitar 1-2 Å. Karena sampel sangat tipis, biasanya kita tidak melihat atom secara
individual. Alih-alih pencitraan dengan modus resolusi tinggi dari gambar mikroskop kisi
kristal dari suatu material sebagai pola interferensi antara ditransmisikan dan berkas
terdifraksi.

Hal ini memungkinkan seseorang untuk mengamati garis planar dan cacat, batas butir,
interface, dll dengan resolusi skala atom. mode pencitraan mikroskop Bright field / dark
field, yang beroperasi di antara pembesaran, dikombinasikan dengan difraksi elektron,
juga sangat berharga untuk memberikan informasi tentang morfologi, kristal tahapan, dan
cacat pada material. Akhirnya mikroskop dilengkapi dengan lensa pencitraan khusus
yang memungkinkan untuk pengamatan micromagnetic domain struktur di bidang
lingkungan bebas. TEM juga mampu membentuk elektron yang terfokus pada probe,
sekecil 20A, yang dapat diposisikan pada fitur yang sangat bagus dalam sampel untuk
informasi atau microdiffraction analisis x-ray untuk informasi komposisi (Sofyan,
Bondan:2008).

4. Manfaat Transmission Electron Microscopy (TEM)

Manfaat dari TEM adalah menangkap dan menghasilkan sinyal-sinyal. Sinyal utama
yang dapat ditangkap atau dihasilkan dari TEM cukup banyakantara lain:

a. Diffraction Contrast
Dipakai untuk mengkarakterisasi Kristal, digunakan untuk menganalisa defek, endapan,
ukuran butiran dan distribusinya.

b. Phase Contrast

Dipakai untuk menganalisa kristalin material (defek, endapan, struktur

interfasa,pertumbuhan kristal)

c. Mass/Thickness Contrast

Dipakai untuk karakterisasi bahan amorf berpori, polimer, material lunak (biologis)

d. Electron Diffraction

e. Characteristic X-ray (EDS)

f. Electron Energy Loss Spectroscopy (EELS + EFTEM)

g. Scanning Transmission Electron Microscopy (STEM) (Ruska, Ernest:1986).

5. Aspek Fisis dari Transmission Electron Microscopy

Dari resolusi yang dimiliki oleh scanning TEM/STEM sebesar 200 kV dapat
dihasilkan pancaran electron dengan panjang gelombang 0.0025 nm. Dengan
demikian karakterisasi nano sekarang ini sudah sangat maju, karena kita dapat
melihat struktur kristal dari material. dalam perkembangan teknologi saat ini, yang
dibutuhkan adalah improvisasi alat/device. Untuk lebih mendapatkan material yang
secara makroskopis unggul dan efisien dari segi sifat listrik maupun optisnya, maka
modifikasi dan analisis nano memegang peranan yang penting. Ketikakita
menganalisis material dalam ukuran nano, maka kita akan melihat bagaimana
distribusi dari elektron yang terlihat dari image yang yang diperoleh (menggunakan
STEM/TEM, FESEM, High Resolution TEM, SEM, dan AFM).
Para ilmuwan Fisika, Kimia dan termasuk ilmuwan dalam bidang material elektronik
saat ini tengah berusaha menciptakan material untuk menghasilkan material yang
berguna dalam industri optoelektronik. Tentu dasarnya adalah teknologi
 semikonduktor yang sudah dikenal lama. Dalam perkembangannya, teknologi
semikonduktor mampu menghasilkan dioda, lalu transistor bahkan yang lebih
kompleks lagi yaitu mikroprosesor. Peralatan/Devices tersebut sangat berperan dalam
penemuan dan pembuatan piranti elektronik untuk komputer, handphone, dsb.
Analisis nano berperan cukup penting untuk mengimprove metode-metode yang
digunakan saat ini. Analisis tersebut tidak hanya digunakan para eksperimentalis saja,
namun juga para teoritis yang menggunakan first principle mengacu pada persamaan
Schrodinger, bandstructure, fungsi gelombang Bloch, nearly free electron model,
density functional theory, dsb untuk memprediksikan besar energi yang dapat
dihasilkan oleh material (Oktaviana,Aptika:2009).

6. Kelebihan dan Kekurangan TEM

8. Kelebihan dan Kekurangan Transmission Electron Microscopy (TEM)

a. Kelebihan

• Dengan TEM, maka gambar yang kita hasilkan akan memiliki tingkat resolusi
yang jauh lebih tinggi daripada mikroskop cahaya. Kita dapat melihat sesuatu
yang memiliki ukuran 10.000 kali lebih kecil daripada ukuran objek terkecil
yang bisa terlihat di mikroskop cahaya.
• Pada perbesaran kecil, gambar TEM akan kontras karena absorbsi elektron pada
material akibat dari ketebalan dan komposisi material. Pada perbesaran tinggi,
maka gambar yang dihasilkan akan menampilkan data yang lebih jelas pada
analisa struktur kristal dan lainnya.

b. Kekurangan

• Persiapan sampel untuk TEM umumnya memerlukan lebih banyak waktu dan
pengalaman daripada kebanyakan teknik karakterisasi lainnya.
• Sebuah spesimen TEM tebalnya mendekati 1000Å atau kurang dalam ketebalan
di daerah tertentu. Seluruh spesimen harus sesuai ke dalam diameter 3mm dan
dengan ketebalan kurang dari sekitar 100 mikron.
• Banyak material memerlukan persiapan sampel yang lebih rumit untuk
menghasilkan sebuah sampel yang cukup tipis agar elektron transparan, yang
membuat analisis TEM yang relatif memakan waktu proses dengan peletakan
sampel yang kecil.
• Struktur sampel juga mungkin berubah selama proses persiapan. Juga bidang
pandang relatif kecil, meningkatkan kemungkinan bahwa daerah dianalisis
mungkin tidak menjadi ciri khas dari seluruh sampel. Ada potensi pula sampel
rusak oleh berkas elektron.
 BAB III

PENUTUP

A. Kesimpulan

Mikroskop Elektron ini dibuat dengan didasarkan pada teori gelombang partikel de
Broglie dan percobaan elektron yang dipercepat dalam suatu kolom elektromagnetik.
TEM mempunyai resolusi yang lebih baik daripada Mikroskop Optic. Hal ini
dikarenakan TEM menggunakan energi yang besar sehingga menghasilkan panjang
gelombang yang lebih pendek. Mikroskop Electron pertama memiliki resolusi hingga 100
nm atau 2 kali lebih baik dari Mikroskop Optic

TEM bekerja dengan prinsip menembakkan elektron ke lapisan tipis sampel, yang
selanjutnya informasi tentang komposisi struktur dalam sample tersebut dapat terdeteksi
dari analisis sifat tumbukan, pantulan maupun fase sinar elektron yang menembus lapisan
tipis tersebut. Dari sifat pantulan sinar elektron tersebut juga bisa diketahui struktur
kristal maupun arah dari struktur kristal tersebut. Bahkan dari analisa lebih detail, bisa
diketahui deretan struktur atom dan ada tidaknya cacat (defect) pada struktur tersebut.
Hanya perlu diketahui, untuk observasi TEM ini, sample perlu ditipiskan sampai
ketebalan lebih tipis dari 100 nanometer.
 DAFTAR PUSTAKA

Farosyid22. 2018. Prinsip Kerja Transmission Electron Microscopy (TEM) dan Perbedaannya
dengan Scanning Electron Microscopy.

https://materialcerdas.wordpress.com/teori-dasar/transmission-electron-microscopy-tem/

Wikipedia. Mikroskop Eektron Transmisi (TEM)

2. Prinsip kerja dan komponen-komponen yang terdapat pada TEM

- Prinsip Kerja TEM

Prinsip kerja dari TEM secara singkat adalah sinar elektron mengiluminasi spesimen dan
menghasilkan sebuah gambar diatas layar pospor. Gambar dilihat sebagai sebuah proyeksi dari
spesimen. Adapun prinsip kerja dari bagian-bagian TEM adalah sebagai berikut:

1. Electron source : Menghasilkan elektron monokromatik.

2. Condensor ions : Memfokuskan berkas elektron.

3. Condensor aperture : Mengurangi intensitas sinar dengan menyaring elektron dari beam.

4. Objective lens : Memfokuskan berkas.

5. Objective aperture : Meningkatkan Kontras dengan menghalangi difraksi elektron.

6. Projector lens : Memperbesar gambar.

7. Screen : Melihat hasil gambar.

- Komponen yang terdapat dalam TEM

Bagian-bagian dari TEM ditunjukkan pada gambar 2 :

Berikut ini adalah bagian-bagian dari TEM :

• Virtual Source di bagian atas mewakili senapan elektron, yang berfungsi menghasilkan
elektron monokromatik.
• Lensa kondensor yaitu aliran elektron difokuskan pada berkas yang kecil, tipis dan
koheren dengan menggunakan lensa kondensor 1 dan 2. Lensa 1 (biasanya dikontrol oleh
tombol "spot size”) sangat menentukan ukuran dari besarnya aliran mengenai sampel.
Lensa kedua (biasanya dikontrol tombol “intensitas/brightness”) yang mengubah ukuran
spot pada sampel.
• Berkas dibatasi oleh aperture dari kondensor (biasanya dapat dipilih pengguna),
merobohkan sudut tinggi elektron (yang jauh dari sumbu optik, garis putus-putus di
tengah-tengah). Aperture Terdiri dari disc logam kecil yang cukup tebal untuk mencegah
elektron dari melewati disc, sementara mengijinkan aksial electron.

Fungsi apertures:
- Mengurangi intensitas sinar elektron disaring dari balok, yang mungkindiinginkan dalam kasus
sampel berkas sensitif.

- Penyaringan ini melepaskan elektron yang tersebar. d. Berkas elektron menumbuk spesimen
kemudian, bagian-bagiannya ditransmisikan.

• Bagian yang ditransmisikan difokuskan oleh lensa objektif menjadi sebuah gambar.
• Tujuan dan pilihan opsional logam Area aperture dapat membatasi sinar. Objective
aperture meningkatkan kontras dengan menghalangi difraksi elektron yang high angle,
yang dipilih aperture memungkinkan penggunauntuk secara berkala memeriksa difraksi
elektron oleh atom dalam sampel.
• Gambar selanjutnya terus melalui intermediate dan lensa proyektor, yang diperbesar
sepanjang jalan.
• Gambar-gambar membentur layar fosfor dan cahaya yang dihasilkan memungkinkan
pemakai untuk melihat gambar. Daerah yang lebih gelap mewakili wilayah yang
elektronnya lebih sedikit sedangkan daerah yang lebih terang mewakili electron yang
lebih banyaki (mereka lebih tipis atau kurang padat) (Oktaviana,Aptika:2009)
 C Journal of
Carbon Research

Review
Transmission Electron Microscopy of Carbon:
A Brief History
Peter J. F. Harris
Electron Microscopy Laboratory, Department of Chemistry, University of Reading, Whiteknights,
Reading RG6 6AF, UK; p.j.f.harris@reading.ac.uk; Tel.: +44-118-378-6118

Received: 21 December 2017; Accepted: 8 January 2018; Published: 12 January 2018

Abstract: Transmission electron microscopy (TEM) has been used in the study of solid carbon
since the 1940s. A number of important forms of carbon have been discovered through the use of
TEM, and our understanding of the microstructure of carbon has largely been gained through the
application of TEM and associated techniques. This article is an attempt to present an historical
review of the application of TEM to carbon, from the earliest work to the present day. The review
encompasses both graphitic carbon and diamond, and spectroscopic techniques are covered, as well
as imaging. In the final section of the review, the impact of aberration-corrected TEM on current
carbon research is highlighted.

Keywords: transmission electron microscopy; graphite; diamond; graphene; carbon nanotubes

1. Introduction
Solid carbon exists in a huge variety of different forms, including graphite, diamond, graphene,
nanotubes, glassy carbon, coke, and char. Much of what we know about the microstructure of these
materials has come from the application of transmission electron microscopy. While X-ray diffraction
can provide more accurate crystallographic information, and spectroscopic techniques can be used
to determine the overall order of the carbon and the sp2 /sp3 ratio, transmission electron microscopy
(TEM) has an unrivalled ability to reveal the microscopic structure, potentially down to the atomic
level. This article aims to trace the history of TEM studies of carbon, from the earliest work in the 1940s
to current research using aberration-corrected microscopes. An attempt is made to identify landmarks
in the field in 20 year periods beginning in 1940. To begin, a brief outline of the history of transmission
electron microscopy is given.

2. The Development of Transmission Electron Microscopy

Max Knoll and Ernst Ruska of the Berlin Technische Hochschule demonstrated the first
transmission electron microscope in 1931 [1], and in 1933 achieved a resolution greater than that
of light with this microscope. Working at Siemens, Ruska helped to develop the first commercial TEM
in 1939. At the same time, Otto Scherzer in Darmstadt was laying the basis for the theory of electron
optics [2]. After the war, a number of companies developed commercial TEMs, notably JEOL in Japan
and Philips in Europe, and the technique grew in importance in both biology and materials science.
Biological applications of TEM are outside the scope of this review, but a few milestones in TEM of
materials will be mentioned. In 1949 Robert Heidenreich of Bell Labs pioneered the study of metals by
TEM, using an electrolytic method to prepare sufficiently thin specimens [3]. Seminal work on defects
in metals was subsequently carried out by Peter Hirsch and colleagues in Cambridge who reported
the first observations of moving dislocations in aluminium [4] and by Walter Bollman of the Battelle
Laboratory in Geneva, who observed dislocations in stainless steel [5].
In 1956 James Menter, working at the Tube Investments research labs near Cambridge, obtained
the first direct lattice images of crystals [6]. The specimens he imaged were thin crystals of copper

C 2018, 4, 4; doi:10.3390/c4010004 www.mdpi.com/journal/carbon

C 2018, 4, 4 2 of 17

and platinum phthalocyanine, both of which have relatively large lattice spacings, of the order of
1.2 nm. Tsutomu Komoda and colleagues from the Hitachi Labs in Tokyo reported similar images in
1958 [7]. In 1965, Komoda recorded lattice images with a spacing of 0.235 nm from thin films of gold [8],
while the first lattice images of graphite were obtained by Heidenreich and colleagues in 1968 [9],
as discussed below. It is important to recognise, however, that most of these early lattice images were
not directly interpretable in terms of the real crystal structure. True “structure imaging” had to await
the development, in the 1970s and 1980s, of improved electron lenses and of accompanying computer
techniques for image simulation.
An experimental scanning transmission electron microscope (STEM) had been built by Manfred
von Ardenne in Berlin before the war [10]. However, it was the work of Albert Crewe at the University
of Chicago in the late 1960s that led to the development of STEM as a practical technique. Crewe
employed a field emission gun to give the coherent and intense source of electrons needed for STEM.
He also developed an annular dark field detector, and using this detector was able to image individual
heavy atoms [11]. Commercial STEMs became available in the 1970s. These early instruments were
generally dedicated high vacuum microscopes. Today it is more usual for a scanning unit to be
incorporated into a conventional TEM.
Another technique associated with TEM should be mentioned. Electron energy loss spectroscopy
(EELS) involves analysing the energy distribution of electrons that have passed through a TEM
specimen [12]. It is particularly useful for light element analysis, and can provide information about
bonding and oxidation state. Since the early 1990s, EELS has been increasingly used to study both sp2
and sp3 carbon and has helped to provide answers to some long-standing issues in carbon science.
By the mid-1990s, progress in improving the resolution of conventional and scanning transmission
electron microscopes had all but drawn to a halt, and it was clear that some major innovations would be
needed if further improvements were to be made. Scherzer had realised in the 1930s that the resolution
of electron lenses was ultimately limited by spherical and chromatic aberration. Although attempts
had been made over the years to design correctors that would compensate for these aberrations,
none were completely successful. The development of fully effective aberration correctors in the
late 1990s by scientists including Harald Rose (a student of Scherzer), Maximilian Haider, and Knut
Urban was therefore a hugely significant advance [13]. Distances smaller than 0.1 nm could now be
resolved by both TEM and STEM. As discussed in Section 3.4 below, few areas have benefitted more
from this new generation of microscopes than carbon science. More detailed historical reviews of
TEM, particularly as applied to materials science, and of aberration-corrected TEM, can be found in
references [14–17]. A previous review of TEM of carbon, focusing mainly on relatively recent work,
has also been given [18].

3. Landmarks in the Application of TEM to Carbon

3.1. 1940s and 1950s

It appears that carbon black was one of the first carbon materials to be studied in the TEM [19–21].
These early studies established that carbon black consisted of aggregated spheroidal particles, with the
individual particles being typically 50–100 nm in size. Work by Hofmann and Höper [19] showed that
the particles became faceted on heating to 3000 ◦ C. At this time the resolution of the best TEMs was
around 10 nm, so there was no possibility of resolving the individual graphitic planes.
Perhaps the most notable early paper on TEM of carbon was a 1952 study of catalytically grown
carbon filaments by the Russian scientists Radushkevich and Lukyanovich [22]. As can be seen in
Figure 1, their images clearly showed that the filaments were tubular. This is now recognised as the
first observation of the structures now known as carbon nanotubes. However, at the time the article
was hardly noticed by Western scientists. Due to the cold war, access to Russian scientific publications
was limited, and papers in Russian did not generally appear in literature databases. Only very recently
has the achievement of these scientists been fully recognised [23].
C 2018, 4, 4 3 of 17

was
C limited,
2018, 4, 4 and papers in Russian did not generally appear in literature databases. Only 3very
of 17
recently has the achievement of these scientists been fully recognised [23].

Figure
Figure 1.1.Very
Very early
early transmission
transmission electron
electron microscopy
microscopy images
images of hollowof hollow
carbon carbonReproduced
filaments. filaments.
Reproduced with permission from [22]. Nauka
with permission from [22]. Nauka Publishers, 1952.Publishers, 1952.

In 1953, British scientists also published TEM images of carbon “vermicules”, some of which
In 1953, British scientists also published TEM images of carbon “vermicules”, some of which
appeared to be helical, in a Nature paper entitled “An unusual form of carbon” [24]. These structures,
appeared to be helical, in a Nature paper entitled “An unusual form of carbon” [24]. These structures,
which are almost certainly nanotubes, were discovered in studies of carbon deposited on the
which are almost certainly nanotubes, were discovered in studies of carbon deposited on the brickwork
brickwork of blast furnaces. They were apparently formed from the catalytic decomposition of carbon
of blast furnaces. They were apparently formed from the catalytic decomposition of carbon monoxide
monoxide by iron oxide particles in the bricks. The paper had no references, and it is very unlikely
by iron oxide particles in the bricks. The paper had no references, and it is very unlikely that the
that the authors were aware of the earlier Russian work.
authors were aware of the earlier Russian work.
3.2. 1960s and 1970s
3.2. 1960s and 1970s
In 1960, Roger Bacon of the Union Carbide Corporation was carrying out experiments on the
In 1960, Roger Bacon of the Union Carbide Corporation was carrying out experiments on the triple
triple point of carbon using a direct current (DC) carbon arc furnace when he noticed fine filaments
point of carbon using a direct current (DC) carbon arc furnace when he noticed fine filaments growing
growing from the vapour phase on the negative electrode. Examination of the fibres in the TEM
from the vapour phase on the negative electrode. Examination of the fibres in the TEM showed that
showed that they had a scroll-like structure, with diameters ranging from a fraction of a μm to over
they had a scroll-like structure, with diameters ranging from a fraction of a µm to over 5 µm [25].
5 μm [25]. Bacon christened the fibres “graphite whiskers”, and showed that they had exceptional
Bacon christened the fibres “graphite whiskers”, and showed that they had exceptional mechanical
mechanical properties, close to the ideal value for a graphite cylinder. Although the whiskers never
properties, close to the ideal value for a graphite cylinder. Although the whiskers never became
became a commercial product, owing to their high production cost, for many years they were the
a commercial product, owing to their high production cost, for many years they were the strongest
strongest and stiffest carbon fibres available, and in some ways represented a precursor to fullerene-
and stiffest carbon fibres available, and in some ways represented a precursor to fullerene-related
related carbon nanotubes.
carbon nanotubes.
One of the most important applications of graphite over the past 60 years has been as a neutron
One of the most important applications of graphite over the past 60 years has been as a neutron
moderator in nuclear reactors. The very first nuclear reactor, the Chicago “squash court” reactor, used
moderator in nuclear reactors. The very first nuclear reactor, the Chicago “squash court” reactor, used
graphite as a neutron moderator, and many commercial reactors, both gas-cooled and water-cooled,
graphite as a neutron moderator, and many commercial reactors, both gas-cooled and water-cooled,
have used graphite in this way. Understanding the structure and properties of graphite therefore
have used graphite in this way. Understanding the structure and properties of graphite therefore
became a priority for the nuclear industry, particularly in view of the fact that that radiation effects
became a priority for the nuclear industry, particularly in view of the fact that that radiation effects on
on the structure of graphite may have played a role in the Windscale reactor fire of 1957. As a result,
the structure of graphite may have played a role in the Windscale reactor fire of 1957. As a result, much
much important and fundamental work on the structure of graphite was carried out using
important and fundamental work on the structure of graphite was carried out using conventional bright
conventional bright and dark field TEM during the 1960s (e.g., [26–28]), as discussed in reviews by
and dark field TEM during the 1960s (e.g., [26–28]), as discussed in reviews by Amelinckx [29] and
Amelinckx [29] and Thrower [30]. Important studies of graphite reactivity, which also originated in
Thrower [30]. Important studies of graphite reactivity, which also originated in nuclear-related research,
C 2018, 4, 4 4 of 17
C 2018, 4, 4 4 of 17

were also carriedresearch,

nuclear-related out by John
wereMeurig Thomas
also carried outandbycolleagues,
John Meurig firstly
Thomasusingand optical microscopy
colleagues, [31]
firstly and
using
later using TEM [32].
optical microscopy [31] and later using TEM [32].
Another area
Another area ofof carbon
carbon science
science that
that benefitted
benefitted from from nuclear-related
nuclear-related research research isis the
the study
study of of
catalytically-grown carbon tubes. As noted above, these were first
catalytically-grown carbon tubes. As noted above, these were first observed in 1952 by Russian observed in 1952 by Russian
scientists, but
scientists, butlittle
littlefurther
furtherworkworkwas was done
done in in
thisthis
area area until
until the the studies
studies of R.T.K.
of R.T.K. ”Terry”
”Terry” Baker Baker
and
and colleagues at the UK’s Atomic Energy Research Establishment,
colleagues at the UK’s Atomic Energy Research Establishment, from about 1970. Baker was from about 1970. Baker was
investigating the
investigating theformation
formationofofcarboncarbon deposits
depositson onnuclear fuel-pins
nuclear fuel-pinsin gas-cooled reactors,
in gas-cooled and inand
reactors, order
in
to model
order to these
model processes
these he employed
processes hecontrolled
employedatmospherecontrolledtransmission
atmosphereelectron microscopy
transmission [33].
electron
In this technique,
microscopy [33]. Inwhich
this had been pioneered
technique, which had by been
Marton as early as
pioneered by 1935
Marton[34],asa differential
early as 1935 pumping
[34], a
system allows the specimen to be exposed to relatively high gas pressures
differential pumping system allows the specimen to be exposed to relatively high gas pressures while while being heated. Baker
used this
being method
heated. Bakerto directly
used this observe
method thetogrowth
directly of observe
filamentous carbon by
the growth of the catalytic decomposition
filamentous carbon by the
of hydrocarbons on metal particles, gaining important insights
catalytic decomposition of hydrocarbons on metal particles, gaining important into the growth mechanism.
insightsAlthough
into the
Baker’s mechanism.
growth work was aimed at preventing
Although Baker’s carbon
work was filament
aimed formation,
at preventing other workers, notablyformation,
carbon filament Morinobu
Endo workers,
other [35], suggested
notably that the filaments
Morinobu Endo could be valuable
[35], suggested thatmaterials
the filamentsin their ownbe
could right. The discovery
valuable materials
in their own right. The discovery of fullerene-related nanotubes by Iijima in 1991 fundamental
of fullerene-related nanotubes by Iijima in 1991 (see below) stimulated a renewed burst of (see below)
work on the
stimulated growth and
a renewed structure
burst of catalytically-grown
of fundamental work on the growth carbon andfilaments,
structureand much of this work
of catalytically-grown
drew on Baker’s pioneering studies.
carbon filaments, and much of this work drew on Baker’s pioneering studies.
A major
A major breakthrough
breakthrough in in TEM
TEM of of carbon
carbon came
came in in 1968
1968 when
when the the first
first lattice
lattice images
images of of graphitic
graphitic
carbon were
carbon were obtained
obtained by by Robert
Robert Heidenreich
Heidenreich of of Bell
Bell Labs
Labs and
and colleagues
colleagues [9]. Images of
[9]. Images of graphitized
graphitized
carbon black were reported in which the approximately 0.34 nm spacing
carbon black were reported in which the approximately 0.34 nm spacing was clearly visible. A was clearly visible. A typical
typical
image of
image of graphitized
graphitized carbon
carbon black,
black, taken
taken aa few
few years
years later
later by
by Ban
Ban[36],
[36], isis shown
shown in in Figure
Figure 2.2. The
The ability
ability
to resolve graphitic structure directly prompted a rapid expansion of TEM work on sp 2 -based carbon
to resolve graphitic structure directly prompted a rapid expansion of TEM work on sp -based carbon 2

materials, including
materials, including carbon
carbon fibres
fibres [37],
[37], glassy
glassy carbon
carbon [38][38] microporous
microporous carbon carbon [39],
[39], and
and coal
coal [40].
[40].
Several reviews
Several reviews of of these
these early
early studies
studies have
have been
been given
given [36,41,42].
[36,41,42].

Figure 2. Early lattice image of carbon black, by Ban. Reproduced with permission from [36]. Royal
Figure 2. Early lattice image of carbon black, by Ban. Reproduced with permission from [36]. Royal
Society of Chemistry, 1972.
Society of Chemistry, 1972.

The study of diamond by transmission electron microscopy was pioneered in 1962 by Trevor
EvansThe
andstudy of diamond
Cornelius Phaal ofby transmission
Reading electron
University [43]. microscopy
These workers was pioneered
showed in 1962 diamonds
that natural by Trevor
Evans and Cornelius Phaal of Reading University [43]. These workers showed that natural
could be thinned by oxidation to the point where imaging in the TEM became possible. In this way, diamonds
couldachieved
they be thinnedthe by oxidation
first images oftoplatelets
the pointonwhere imaging
the {100} latticeinplanes
the TEM became
in type possible. an
Ia diamonds, In this way,
example
they
of achieved
which the first
is shown images
in Figure of platelets
3. Such defectson the absent
were {100} lattice
in type planes in type Ia
II diamonds, diamonds,
but both typesancontained
example
of which is shown in Figure 3. Such defects were absent in type II diamonds, but both types
dislocations (diamonds are classified into different types depending on the kind of impurities they contained
dislocations
contain). The(diamonds are classified
precise nature into different
of the platelets, which hadtypes depending
been on the by
first postulated kind ofFrank
F.C. impurities they
in 1956 to
explain anomalous features in X-ray diffraction patterns of type Ia diamond [44], was a subject of
controversy for many years. Evans and Phaal initially suggested that the platelets contained nitrogen,
C 2018, 4, 4 5 of 17

contain). The precise nature of the platelets, which had been first postulated by F.C. Frank in 1956
to explain
C 2018, 4, 4 anomalous features in X-ray diffraction patterns of type Ia diamond [44], was a subject 5 of of
17
controversy for many years. Evans and Phaal initially suggested that the platelets contained nitrogen,
which is thethe main
main impurity
impurity in
in type
type Ia
Ia diamonds.
diamonds. A detailed structural model of nitrogen-containing
platelets
platelets was proposed by Andrew Lang of
was proposed by Andrew Lang of the University
University of Bristol in 1964 [45]. However, later work
cast doubt on the idea that nitrogen was a major major component
component of platelets (e.g., [46]), and the issue
remained unresolved.
unresolved.

Figure 3. One of the first TEM images of platelets in type Ia diamond, from a 1962 paper by Evans &
Figure 3. One of the first TEM images of platelets in type Ia diamond, from a 1962 paper by Evans &
Phaal. Reproduced with permission from [43]. Royal Society, 1962.
Phaal. Reproduced with permission from [43]. Royal Society, 1962.

Another kind of defect in type Ia diamond discovered using transmission electron microscopy
AnotherThese
are voidites. kind of defect inwere
structures type first
Ia diamond
observeddiscovered
by Robert using transmission
Stephenson, a Ph.D.electron
studentmicroscopy
at Reading
are
in 1978 [47]. Voidites are tiny {111}-faceted cavities that lie in {100} planes in circumstances Reading
voidites. These structures were first observed by Robert Stephenson, a Ph.D. student at strongly
in 1978 [47].that
suggesting Voidites are tiny
they result {111}-faceted
from cavities that
the decomposition lie in {100}
of platelets. planes
Further in circumstances
studies strongly
of both voidites and
suggesting that they result
platelets are discussed below.from the decomposition of platelets. Further studies of both voidites and
platelets are discussed below.
3.3. 1980s and 1990s
3.3. 1980s and 1990s
These two decades saw a revolution in carbon science, which was initiated by the discovery of
These two decades saw a revolution in carbon science, which was initiated by the discovery
C60 in 1985 [48]. Although transmission electron microscopy was not involved in the initial discovery
of C60 in 1985 [48]. Although transmission electron microscopy was not involved in the initial
of C60, it played an important role in subsequent developments. One of the first of these was the
discovery of C60 , it played an important role in subsequent developments. One of the first of these
discovery of fullerene-related carbon nanotubes by Sumio Iijima, of the NEC laboratories in Japan, in
was the discovery of fullerene-related carbon nanotubes by Sumio Iijima, of the NEC laboratories in
1991 [49]. Prompted by the demonstration that C60 could be produced in bulk in a simple arc-
Japan, in 1991 [49]. Prompted by the demonstration that C60 could be produced in bulk in a simple
evaporation apparatus [50], Iijima embarked on a detailed TEM study of the soot produced by their
arc-evaporation apparatus [50], Iijima embarked on a detailed TEM study of the soot produced by their
technique. When he examined the hard, cylindrical deposit that had formed on the graphite cathode
technique. When he examined the hard, cylindrical deposit that had formed on the graphite cathode
after arc-evaporation, he found that this was filled with multiwalled carbon nanotubes (MWCNTs),
after arc-evaporation, he found that this was filled with multiwalled carbon nanotubes (MWCNTs),
much more perfect than those produced by catalysis. Some images taken from Iijima’s 1991 Nature
much more perfect than those produced by catalysis. Some images taken from Iijima’s 1991 Nature
paper [49] are shown in Figure 4a. The publication of Iijima’s paper stimulated huge interest, and
paper [49] are shown in Figure 4a. The publication of Iijima’s paper stimulated huge interest, and many
many important advances followed, mostly involving TEM.
important advances followed, mostly involving TEM.
One of the characteristic features of nanotubes produced by arc-evaporation is that they are
One of the characteristic features of nanotubes produced by arc-evaporation is that they are almost
almost always closed at both ends with caps that can have a variety of structures. In 1992, Iijima and
always closed at both ends with caps that can have a variety of structures. In 1992, Iijima and Toshinari
Toshinari Ichihashi published images of caps displaying a “bill-like” morphology, as shown in Figure
Ichihashi published images of caps displaying a “bill-like” morphology, as shown in Figure 4b [51].
4b [51]. In these structures it is believed that a heptagonal ring occurs at the saddle point, labelled
In these structures it is believed that a heptagonal ring occurs at the saddle point, labelled “B” in
“B” in the figure. These images represented the first evidence for 7-membered rings in graphitic
materials. In 1993, Iijima’s group and a team led by Donald Bethune at the IBM Almaden Research
Center in California independently reported the synthesis of single-walled nanotubes (SWCNTs)
[52,53]. These were discovered while carrying out arc-evaporation experiments using graphite
electrodes impregnated with metals. This was found to produce single-walled tubes with diameters
C 2018, 4, 4 6 of 17

the figure. These images represented the first evidence for 7-membered rings in graphitic materials.
In 1993, Iijima’s group and a team led by Donald Bethune at the IBM Almaden Research Center
in California independently reported the synthesis of single-walled nanotubes (SWCNTs) [52,53].
These were discovered while carrying out arc-evaporation experiments using graphite electrodes
C 2018, 4, 4 6 of 17
impregnated
C 2018, 4, 4
with metals. This was found to produce single-walled tubes with diameters of 6the order
of 17
of 1 nm entangled
of the order of with amorphous
1 nm entangled soot
with and residual
amorphous particles
soot and of metal
residual orof
particles metal
metalcarbide.
or metalMicrographs
carbide.
offrom
the order
takenMicrographs oftaken
1 nmfrom
the Bethune entangled
paper with
are amorphous
shown in soot
Figure and
5. residual
This particles
discovery of metal
gave an
the Bethune paper are shown in Figure 5. This discovery gave or metal carbide.
important boost to
an important
Micrographs
nanotube
boostscience. taken from
to nanotube science. the Bethune paper are shown in Figure 5. This discovery gave an important
boost to nanotube science.

Figure 4. (a)4.Some
Figure (a) Someof Iijima’s first
of Iijima’s images
first imagesofofmultiwalled nanotubes.Reproduced
multiwalled nanotubes. Reproduced withwith permission
permission
Figure
from from 4.
[49]. [49]. (a)
Springer Some of Iijima’s
Nature,
Springer Nature, first
1991; images
1991;(b) of multiwalled
(b)Multiwalled
Multiwalled nanotubenanotubes.
cap.“A”
nanotube cap. Reproduced
“A” with
indicates
indicates permission
position
position of single
of single
from “B”
pentagon; [49]. indicates
pentagon; Springer
“B” Nature,
indicates
probable 1991;
probable (b) Multiwalled
position
position ofofsingle nanotubeReproduced
single heptagon.
heptagon. cap. “A” indicates
Reproduced with positionfrom
permission
with of single
permission [51]. [51].
from
pentagon;Nature,
Springer “B” indicates
1992. probable position of single heptagon. Reproduced with permission from [51].
Springer Nature, 1992.
Springer Nature, 1992.

Figure 5. Images from the work of Bethune et al. showing single-walled carbon nanotubes produced
Figure
Figure
by 5. Images
Images fromfrom
5.co-vaporization the work ofand
the work
of graphite Bethune
cobalt.etReproduced
of Bethune al. showing
et al. showingsingle-walled
permissioncarbon
single-walled
with carbon nanotubes
nanotubes
from [53]. produced
Nature, by
produced
Springer
by co-vaporization
co-vaporization
1993. of graphite and cobalt. Reproduced with permission from [53]. Springer
of graphite and cobalt. Reproduced with permission from [53]. Springer Nature, Nature,1993.
1993.
Another very active area of research during the 1990s involved opening and filling carbon
Another
nanotubes. very
The firstactive area of research
demonstration during
of nanotube the was
filling 1990sgiven
involved opening
by Pulickel and filling
Ajayan carbon
and Iijima in
nanotubes. The first demonstration of nanotube filling was given by Pulickel Ajayan and Iijima in
C 2018, 4, 4 7 of 17

Another very active area of research during the 1990s involved opening and filling carbon
C 2018, 4, 4 7 of 17
nanotubes. The first demonstration of nanotube filling was given by Pulickel Ajayan and Iijima in
1993 [54]. In
1993 [54]. Inthis
thiswork,
work,particles
particles ofof lead
lead were
were deposited
deposited ontoonto multiwalled
multiwalled tubestubes
in a in a vacuum
vacuum and
and then
then heated in air at 400 ◦ C, a temperature sufficient to melt the lead. Examination of the resulting
heated in air at 400 °C, a temperature sufficient to melt the lead. Examination of the resulting material
material
in a TEMin a TEMthat
showed showed
smallthat small proportion
proportion of the tubesof had
the tubes had beenfilled.
been partially partially
A shortfilled.
timeA later,
shortmore
time
later, more and
controlled controlled
efficientand efficientofmethods
methods openingof opening multiwalled
multiwalled nanotubes,nanotubes, using oxidation,
using oxidation, were
were described
described by Edman Tsang and colleagues (including the present author) at
by Edman Tsang and colleagues (including the present author) at Oxford [55], and by a team led Oxford [55], and by a teamby
led by Ajayan [56]. The Oxford group subsequently showed that
Ajayan [56]. The Oxford group subsequently showed that MWCNTs could be opened by treating MWCNTs could be opened by
treating with nitric acid, and that tubes opened in this way could be partially filled
with nitric acid, and that tubes opened in this way could be partially filled with a variety of materials with a variety of
materials [57]. Figure 6, taken from this work, shows a crystal of metallic nickel
[57]. Figure 6, taken from this work, shows a crystal of metallic nickel inside a multiwalled tube. inside a multiwalled
tube.
Jeremy Jeremy
SloanSloan and colleagues
and colleagues fromfrom Oxford
Oxford showed
showed in 1998
in 1998 that
that SCWNTscan
SCWNTs canbe beopened
opened andand filled
filled
using techniques similar to those employed for MCWNTs [58]. At around the
using techniques similar to those employed for MCWNTs [58]. At around the same time, Brian Smith, same time, Brian Smith,
Marc
Marc Monthioux,
Monthioux, and and David
David LuzziLuzzi used
used aa pulsed
pulsed laser
laser vaporization technique to
vaporization technique to prepare
prepare SCWNTs
SCWNTs
partially
partially filled
filled with
with C C60 molecules [59]. This remarkable work prompted other groups to explore the
60 molecules [59]. This remarkable work prompted other groups to explore the
encapsulation
encapsulation of larger fullerenes and
of larger fullerenes and ofof metallofullerenes
metallofullerenes in in single-walled
single-walled tubes
tubes (see(see next
nextsection).
section).

Figure 6. Nanotube partially filled with metallic nickel prepared by hydrogen reduction of a NiO
Figure 6. Nanotube partially filled with metallic nickel prepared by hydrogen reduction of a NiO
precursor. Reproduced with permission from [57]. Springer Nature, 1994.
precursor. Reproduced with permission from [57]. Springer Nature, 1994.

Daniel Ugarte, working at the Ecole Polytechnique Fédérale de Lausanne in Switzerland, made
Daniel Ugarte,
an extraordinary working
discovery inat the Ecole
1992. He foundPolytechnique Fédérale
that irradiating carbondenanotubes
Lausanneand in Switzerland,
nanoparticlesmadewith
an extraordinary discovery in 1992. He found that irradiating carbon nanotubes
an intense beam of electrons in a TEM caused the structures to evolve into almost perfect spheres and nanoparticles
with an intense
apparently madebeam
up ofofconcentric
electrons fullerenes.
in a TEM caused the structures
In a paper published toin evolve
Nature into
[60], almost
Ugarteperfect spheres
christened the
apparently made up of concentric fullerenes. In a paper published in
particles “carbon onions”. They differ from the carbon nanoparticles that accompany nanotubesNature [60], Ugarte christened
the particles
produced by “carbon onions”.the
arc-evaporation: They differ
latter fromhave
usually the relatively
carbon nanoparticles that accompany
large inner cavities, while onionsnanotubes
appear
produced by arc-evaporation: the latter usually have relatively large inner
to have a C60 molecule at the centre. Carbon onions should therefore be considered a distinct species cavities, while onions
appear to have a C60 molecule at the centre. Carbon onions should therefore be considered a distinct
of carbon.
speciesTheofdiscovery
carbon. of fullerenes and of fullerene-related carbons stimulated huge interest. As well as
researching the newof
The discovery fullerenes
materials and of fullerene-related
themselves, a number of workers carbons stimulated
were prompted hugeto interest. As well
take a fresh look as
at
researching the new materials themselves, a number of workers were prompted
much “older” forms of carbon. In 1997, the present author, with Tsang, published a high resolution to take a fresh look at
much “older” forms of carbon. In 1997, the present author, with Tsang, published
TEM study of some non-graphitizing carbons [61]. These are carbons that cannot be transformed into a high resolution
TEM studygraphite
crystalline of some non-graphitizing
even at temperatures carbons [61].°C
of 3000 These
and are carbons
above. Theythatare cannot
also knownbe transformed into
as chars. Their
crystalline graphite even at temperatures of 3000 ◦ C and above. They are also known as chars. Their
precise structure, and the reasons for their resistance to graphitization, has been a matter of debate since
precise structure,
the classic work ofand the reasons
Rosalind Franklin for in
their
1951resistance to graphitization,
[62]. In our 1997 work, wehas been athat
showed matter of debate
heating non-
since the classic work of Rosalind Franklin in 1951 [62]. In our 1997 work,
graphitizing carbons to 2600 °C could result in the formation of closed carbon nanoparticles, which we showed that heating
non-graphitizing
were apparently carbons to 2600in◦ Cstructure,
fullerene-like could result in the formation
as shown in Figureof7.closed
Basedcarbon
on these nanoparticles,
observations,which
we
were apparently fullerene-like in structure, as shown in Figure 7. Based
proposed a new model for the structure of non-graphitizing carbons consisting of curved carbon on these observations, we
proposed a new model
sheets, in which for the
pentagons and structure
heptagons of non-graphitizing
are dispersed randomlycarbons throughout
consisting ofnetworks
curved carbon sheets,
of hexagons
in
to create a microporous structure. We believe that this model helps to explain the properties ofcreate
which pentagons and heptagons are dispersed randomly throughout networks of hexagons to non-
agraphitizing
microporous structure. We believe that this model helps to explain the properties
carbons, and there is growing evidence that it is correct [63] (see also next section). of non-graphitizing
carbons, and there is growing evidence that it is correct [63] (see also next section).
C 2018, 4, 4 8 of 17
C 2018, 4, 4 8 of 17
C 2018, 4, 4 8 of 17

Figure7.7.(a)
Figure (a)Micrograph
Micrographshowing
showing closed
closed structure in polyvinylidene
structure in polyvinylidene chloride
chloride(PVDC)-derived
(PVDC)-derivedcarbon
carbon
Figure 7. (a) Micrograph
◦ showing closed structure in polyvinylidene chloride (PVDC)-derived carbon
heated
heatedatat2600 C; (b)
2600 °C; (b)another
another micrograph
micrograph ofof same
same sample, with arrows
sample, with arrows showing
showing regions
regionsof ofnegative
negative
heated at 2600 °C; (b) another micrograph of same sample, with arrows showing regions of negative
curvature.
curvature.From
From work
work byby
Harris and
Harris Tsang.
and Tsang.Reproduced
Reproduced with permission
with fromfrom
permission [61].[61].
Taylor & Francis,
Taylor 1997.
& Francis,
curvature. From work by Harris and Tsang. Reproduced with permission from [61]. Taylor & Francis,
1997.
1997.
Detailed TEM studies of defects in diamond continued into the 1980s. Figure 8 shows a beautiful
Detailed
micrograph of TEM
Detailed aTEM
type studies of
ofdefects
Ia diamond,
studies defects in
in diamond
taken continued
from a review
diamond continued intothe
of work
into the 1980s.
carried
1980s. outFigure 88shows
at Bristol
Figure shows anda abeautiful
beautiful
Oxford in
micrograph
themicrograph of
late 70s andofearlya type
a type Ia
80s diamond,
Ia [64]. taken
This image
diamond, from
taken fromshows a review
platelets
a review of work
of and carried
workcollapsed
carried out out at Bristol
platelets.
at Bristol The
andand Oxford
stripes
Oxford within
in in
the
the the late
late70s
platelets and
70sare early
early80s
80s[64].
andstacking-fault This
This image
[64].fringes, which
image shows
showsoccurplatelets
because
platelets and
and the collapsed platelets.
plateletsplatelets.
collapsed disrupt the The
The stripeswithin
normal
stripes within
stacking
the
theplatelets
sequence in the
platelets are stacking-fault
crystal,
are creatingfringes,
stacking-fault which
a diffraction
fringes, occur
whichinterference because
occur because theplatelets
effect.
the platelets disruptthe
The controversy
disrupt the normalstacking
concerning
normal stacking
whether
sequence
thesequence in the
plateletsincontain crystal, creating
nitrogen
the crystal, creatingalsoa diffraction interference
continued.interference
a diffraction In 1982, Steven effect. The
effect.Berger controversy
and Stephen
The controversy concerning
Pennycook
concerning whether
of the
whether
the
theplatelets
Cavendish platelets contain
containnitrogen
Laboratory, nitrogen
Cambridge, also continued.
alsopublished In 1982,
continued.results
In 1982, Stevenusing
Steven
obtained Bergeran
Berger and
and Stephen
Stephen
EELS Pennycook
Pennycook
spectrometer ofofthe
attached theto
a Cavendish
Cavendish
scanning Laboratory,
transmission Cambridge,
Laboratory,electron
Cambridge, published
published
microscope results
results
which obtained
obtained
showed thatusingusingan
nitrogen anEELS
EELSpresent
was spectrometer
spectrometer
[65]. John attached
attached
Bruley
totoaMick
and ascanning
scanning
Brown transmission
transmission
from the same electron
electron microscope
microscope
laboratory using which
which showed
showed
the same thatnitrogen
that
technique nitrogen
in 1989 was
was present
present
found [65].John
no[65]. John
detectable
Bruley and Mick Brown from the same laboratory using
nitrogen in platelets [66]. Improvements in TEM technology during the 1980s and 1990s meantno
Bruley and Mick Brown from the same laboratory using the
the same
same technique
technique inin 1989
1989 found
found no
that
detectable
detectable
lattice imaging nitrogen
of thein
nitrogen inplatelets [66].
[66]. Improvements
plateletsstructure
diamond Improvements in TEM
in
became a practical TEMpossibility,
technologyand
technology during
during
thisthethe1980s
1980s
helped toandand1990s
resolve1990s
the
meant that lattice imaging of the diamond structure became a practical
nitrogen-in-platelets issue. In 1995, Fallon, Brown, Barry, and Bruley, using a combination of EELSto
meant that lattice imaging of the diamond became a practical possibility,
possibility, and
and this
this helped
helped to
and
resolvethe
resolve thenitrogen-in-platelets
nitrogen-in-plateletsissue. issue. In 1995, Fallon,
Fallon, Brown,
Brown, Barry,
Barry, and
and Bruley,
Bruley, using
using a acombination
combination
high-resolution TEM [67], showed that the nitrogen concentration differed from platelet to platelet
ofofEELS
and
EELSand
concluded
andhigh-resolution
high-resolutionTEM TEM [67], showed that the
that the most likely [67], the nitrogen
structure for the platelets nitrogen concentration differed
was concentration
a variation of adiffered
from
model that fromplatelet
platelet
had been
to platelet and concluded
to platelet and concluded that the mostthat the most likely structure for the platelets was a variation
structure for the platelets was a variation of a model of a model
proposed by Humble in 1982 [68]. In this model, the platelets consist of an interstitial layer of carbon
thathad
that hadbeen
beenproposed
proposedby by Humble
Humble in in 1982 [68]. In this this model,
model,the theplatelets
plateletsconsist
consistofofananinterstitial
interstitial
atoms pentagonally bonded to the surrounding diamond matrix. The nitrogen is not an essential
layerofofcarbon
layer carbonatomsatomspentagonally
pentagonally bonded bonded to to the
the surrounding
surroundingdiamond diamondmatrix.matrix.The Thenitrogen
nitrogenisisnot not
component of the platelets, but tends to accumulate in the platelets as a result of aggregation of
an essential component of the platelets, but tends to accumulate
an essential component of the platelets, but tends to accumulate in the platelets as a result of in the platelets as a result of
“Aaggregation
centres” (A centres are pairs (Aofcentres
nitrogen areatoms
pairs on adjacent atomic sites in the diamond). Although
aggregation ofof“A “Acentres”
centres” (A centres are pairs of
of nitrogen
nitrogen atoms atoms on onadjacent
adjacentatomic
atomicsites sitesininthethe
thediamond).
precise nature of platelets
Although continues
the precise
precise nature to of
beplatelets
debated continues
today, it seems to be generally accepted that the
diamond). Although the nature of platelets continues to to be
be debated
debatedtoday,
today,ititseems
seemstotobebe
model put forward
generallyaccepted by
acceptedthat Fallon
thatthe et
themodel al.
model put in 1995 is
put forward broadly
forward by correct.
generally by Fallon
Fallon et et al.
al.in in1995
1995isisbroadly
broadlycorrect.
correct.

Figure 8. Image of type Ia diamond from work by Barry et al. showing large platelets. Reproduced
Figure 8. Image of type Ia diamond from work by Barry et al. showing large platelets. Reproduced
with permission
Figure 8. Imagefrom
offrom[64].
type IaRoyal Society,
diamond from1987.
work by Barry et al. showing large platelets. Reproduced
with permission [64]. Royal Society, 1987.
with permission from [64]. Royal Society, 1987.
C 2018, 4, 4 9 of 17
C 2018, 4, 4 9 of 17

The
The nature
nature ofof voidites
voidites was
was investigated
investigated by by aa number
number ofof groups.
groups. An An edge-on
edge-on view
view of of aa voidite
voidite
sheet,
sheet, taken from the review mentioned above [64], is shown in Figure 9. Far from beingitvoid,
taken from the review mentioned above [64], is shown in Figure 9. Far from being void, turnedit
out thatout
turned these
thatdefects are filled
these defects with
are a solid
filled with phase.
a solidJohn
phase.Hutchison and Leslie
John Hutchison andBursill
Leslie reported in 1983
Bursill reported
that the that
in 1983 voidites often displayed
the voidites Moiré patterns
often displayed Moiré [69], and [69],
patterns Barryand[70]Barry
and Hirsch et al.
[70] and [71] suggested
Hirsch et al. [71]
that these were due to the presence of solid nitrogen. Bruley and Brown’s 1989
suggested that these were due to the presence of solid nitrogen. Bruley and Brown’s 1989 EELS EELS study confirmed
study
the presence
confirmed theofpresence
nitrogen ofin nitrogen
voidites [66]. Species[66].
in voidites that Species
would normally
that would be normally
gaseous atberoom temperature
gaseous at room
are solid because
temperature they because
are solid experiencetheya high pressure
experience in the
a high voidites.inVoidites
pressure are believed
the voidites. Voiditestoare
form when
believed
diamonds containing
to form when platelets
diamonds are subducted
containing to depths
platelets of 150 km or
are subducted tosodepths
in the continental
of 150 kmcrust.
or soAtinthese
the
depths, diamonds are metastable and nitrogen is forced out of solid solution.
continental crust. At these depths, diamonds are metastable and nitrogen is forced out of solidThe exsolved nitrogen
then forms
solution. Thevoidites by displacing
exsolved nitrogen thencarbon
formsatoms [72].by displacing carbon atoms [72].
voidites

Figure 9. Voidite sheet in type Ia diamond. Reproduced with permission from [64]. Royal Society,
Figure 9. Voidite sheet in type Ia diamond. Reproduced with permission from [64]. Royal Society, 1987.
1987.

As well as studying defects in natural diamond, Trevor Evans’ group at Reading carried out
As well as studying defects in natural diamond, Trevor Evans’ group at Reading carried out
remarkable
remarkable work
workininwhich
whichthe conditions
the conditions experienced
experienced by diamonds
by diamonds in the
in Earth over millions
the Earth of years
over millions of
were replicated in the laboratory [73]. This was achieved by placing diamond
years were replicated in the laboratory [73]. This was achieved by placing diamond samples in a samples in a specially
designed tetrahedral
specially designed cell, in which
tetrahedral cell, inthey could
which theybecould
subjected to pressures
be subjected up to 9.5
to pressures upGPa while
to 9.5 GPa being
while
heated to temperatures as high as 2500 ◦ C. When synthetic diamonds containing a high concentration
being heated to temperatures as high as 2500 °C. When synthetic diamonds containing a high
of nitrogen atoms
concentration were treated
of nitrogen atomsinwere
this way, all in
treated thethis
types
way,of all
aggregate that
the types of are found in
aggregate natural
that type in
are found la
diamonds
natural typewere produced.were
la diamonds By analysing
produced. theByresults of these
analysing the experiments, Evans
results of these and colleagues
experiments, Evanswere
and
able to draw conclusions about the conditions experienced by diamonds in
colleagues were able to draw conclusions about the conditions experienced by diamonds in thethe Upper Mantle.
Upper
3.4. Mantle.
2000 to Present
The to
3.4. 2000 in-plane
Presentcarbon-carbon bond distance in graphene is 0.142 nm, too small to be resolved in
most conventional TEMs. However, the development of aberration-corrected TEMs meant that the
The in-plane carbon-carbon bond distance in graphene is 0.142 nm, too small to be resolved in
atomic structure of graphene-related carbons could now be directly imaged and, as already noted,
most conventional TEMs. However, the development of aberration-corrected TEMs meant that the
this has had a major impact on carbon science. Much of the AC-TEM work on carbon has involved the
atomic structure of graphene-related carbons could now be directly imaged and, as already noted,
use of relatively low accelerating voltages (60–80 kV), in order to avoid beam damage. It seems that
this has had a major impact on carbon science. Much of the AC-TEM work on carbon has involved
the first application of aberration-corrected TEM to carbon was a study of single-walled nanotubes by
the use of relatively low accelerating voltages (60–80 kV), in order to avoid beam damage. It seems
Nobuo Tanaka of Nagoya University [74]. However, the leading figure in this area, at least in the early
that the first application of aberration-corrected TEM to carbon was a study of single-walled nanotubes
days, was Kazu Suenaga of Japan’s National Institute for Advanced Industrial Science and Technology.
by Nobuo Tanaka of Nagoya University [74]. However, the leading figure in this area, at least in the
In a series of papers beginning in 2007, Suenaga and his colleagues published images of nanotubes
early days, was Kazu Suenaga of Japan’s National Institute for Advanced Industrial Science and
and graphene of a quality that had not been previously seen [75–80]. These provided new insights into
Technology. In a series of papers beginning in 2007, Suenaga and his colleagues published images of
the nature of defects in SWCNTs [75], the structure of molecules encapsulated inside nanotubes [78],
nanotubes and graphene of a quality that had not been previously seen [75–80]. These provided new
and the edge structure of graphene [79,80]. Figures 10 and 11 show examples of the work of the
insights into the nature of defects in SWCNTs [75], the structure of molecules encapsulated inside
Suenaga group. In Figure 10, three micrographs are shown, taken a short time apart, of C80 molecules
nanotubes [78], and the edge structure of graphene [79,80]. Figures 10 and 11 show examples of the
inside a SWCNT [78]. The atomic structures of both the fullerene molecules and the nanotube can be
work of the Suenaga group. In Figure 10, three micrographs are shown, taken a short time apart, of C80
clearly seen, and orientational changes of the fullerene molecules are evident. Figure 11 is taken from
molecules inside a SWCNT [78]. The atomic structures of both the fullerene molecules and the
a 2010 paper by Suenaga and Masanori Koshino entitled “Atom-by-atom spectroscopy at graphene
nanotube can be clearly seen, and orientational changes of the fullerene molecules are evident. Figure
edge” [80]. Here a low-voltage STEM was used to obtain atomic resolution images of a graphene
11 is taken from a 2010 paper by Suenaga and Masanori Koshino entitled “Atom-by-atom
spectroscopy at graphene edge” [80]. Here a low-voltage STEM was used to obtain atomic resolution
C 2018, 4, 4 10 of 17
C 2018,
C 2018, 4,
4, 44 10 of
10 of 17
17

edge
images
imagesusing
of aaan
of annularedge
graphene
graphene darkusing
edge field detector,
using an annular
an anddark
annular to record
dark energy-loss
field detector,
field detector, andnear-edge
and record fine
to record
to structurenear-edge
energy-loss
energy-loss (ELNES)
near-edge
spectra of single
fine structure
fine carbon
structure (ELNES) atoms.
(ELNES) spectra In
spectra of this
of single way, they
single carbon were
carbon atoms. able
atoms. In to
In this investigate
this way,
way, they the
they were electronic
were able
able to and bonding
to investigate
investigate the
the
structures
electronic of
electronic and
andindividual
bonding edge atoms,
bonding structures
structures of aindividual
of remarkable
individual achievement.
edge
edge atoms, aa remarkable
atoms, remarkable achievement.
achievement.

Figure 10. Aberration-corrected

Figure 10. Aberration-corrected TEM
TEM images of D
images of D5d
D -C8080
5d-C
5d fullerenemolecules
fullerene
80fullerene molecules inside
molecules inside (18,1) SWNT,
SWNT, from
(18,1) SWNT, from
work
work by
by Suenaga
work by Suenaga et
Suenaga al. Reproduced
et al. Reproduced with
Reproduced with permission
with permission from
permission from [78].
from American Chemical
[78]. American
American Chemical Society,
Chemical Society, 2007.
Society, 2007.
Triangles
Trianglesindicate
Triangles indicateencapsulated
indicate encapsulatedmolecule
encapsulated moleculeundergoing
molecule undergoingorientational
undergoing orientationalchanges.
orientational changes.
changes.

Figure 11.Imaging
Figure 11.
11. Imaging
Imaging and
andspectroscopy
and spectroscopy
spectroscopyof a graphene
of edge, from
of aa graphene
graphene edge,
edge, work by Suenaga
from
from work by
work byand Koshino.
Suenaga
Suenaga and
andReproduced
Koshino.
Koshino.
with permission
Reproduced with
Reproduced from [80].
with permission Springer
permission from Nature,
from [80]. 2010.
[80]. Springer (a) Unprocessed
Springer Nature,
Nature, 2010.
2010. (a)ADF image
(a) Unprocessed of
Unprocessed ADFsingle graphene
ADF image
image of layer;
of single
single
Atomic positions
graphene layer;
graphene are
layer; Atomic marked
Atomic positionsby circles
positions are in smoothed
are marked
marked by image
by circles
circles in(b). Scale
in smoothed bars,
smoothed image 0.5 nm.
image (b). (d) ELNES
(b). Scale
Scale bars, of
bars, 0.5carbon
0.5 nm.
nm. (d)K
(d)
(1 s) spectra
ELNES
ELNES of taken K
of carbon
carbon at the
K (1 s)colour-coded
(1 s) spectra taken
spectra takenatoms theindicated
at the
at in (b).atoms
colour-coded
colour-coded Green,indicated
atoms blue, andin
indicated red
in spectra
(b).
(b). Green,
Green, correspond
blue, and
blue, and
to
red
redthespectra
spectra sp2 carbon to
normalcorrespond
correspond atom,
theanormal
to the double-coordinated
normal sp atom and
carbon atom,
sp22 carbon atom, a single-coordinated
aa double-coordinated
double-coordinated atom,
atom
atom respectively.
and
and aa single-
single-
These different
coordinated
coordinated states
atom,
atom, of atomic These
respectively.
respectively. coordination
These different
differentare marked
states
states by coloured
of atomic
of atomic arrowsare
coordination
coordination in marked
are (a,b)
markedandby
byillustrated
coloured
coloured
in (c).
arrows in
arrows in (a,b)
(a,b) and
and illustrated
illustrated inin (c).
(c).
CC 2018,
2018, 4,
4, 44 11of
11 of17
17

As well as studying nanotubes and graphene, Suenaga’s group, with the present author, recorded
the firstwell
As as studying nanotubes
aberration-corrected and graphene,
TEM images Suenaga’s carbon
of a microporous group, inwith the[81].
2008 present
The author, recorded
aim of this work
the first aberration-corrected TEM images of a microporous carbon
was to establish whether evidence could be found to support the idea that these carbons containin 2008 [81]. The aim of this work
was to establish
pentagons whether
and other evidence couldrings,
non-six-membered be found to support
in addition the idea Obtaining
to hexagons. that theseatomiccarbons contain
resolution
pentagons and other non-six-membered rings, in addition to hexagons.
images of the fresh carbon proved difficult, so samples of carbon heated to 2000 °C were examined. Obtaining atomic resolution
images ◦ C were examined.
In suchof the fresh
samples, carbon
clear proved
evidence was difficult,
found for so the
samples
presenceof carbon heated to
of pentagonal 2000supporting
rings, the view
In such
that thesamples,
carbonsclear haveevidence was found structure.
a fullerene-related for the presence
Junjie of Guopentagonal rings, supporting
et al. reported the view
aberration-corrected
that
TEMthe carbons
images of have
“fresh” a fullerene-related
microporous carbons structure. Junjie
in 2012 Guo
[82]. et al. non-six-membered
Again, reported aberration-corrected rings were
TEM
found, images
but in of this
“fresh”
casemicroporous carbons in 2012
groups of pentagonal and [82]. Again, non-six-membered
heptagonal carbon rings were rings seen,were
rather found,
than
but in this case groups of pentagonal and heptagonal carbon rings
isolated pentagons. More studies of this kind on microporous carbons, and other “well-known” were seen, rather than isolated
pentagons.
forms of carbon Morewould
studies beof this kind on microporous carbons, and other “well-known” forms of
welcome.
carbon would bethe
Following welcome.
pioneering work of Suenaga and co-workers on the application of aberration-
corrected TEM (AC-TEM) to work
Following the pioneering carbon,of Suenaga
a number andofco-workers
other groups on the
have application
carried out of exceptional
aberration-corrected
work in
TEM (AC-TEM) to carbon, a number of other groups have carried
this field. Workers from Berkeley using the TEAM (Transmission Electron Aberration-Corrected out exceptional work in this field.
Workers
Microscope) from have
Berkeley using the
published TEAM images
beautiful (Transmission
of defectsElectron
and edgeAberration-Corrected
structures in graphene Microscope)
[83,84],have
and
published beautiful images of defects and edge structures in graphene
Jannik Meyer, who was a member of the Berkeley group, has continued to study graphene using AC- [83,84], and Jannik Meyer, who
was
TEM a member of the Berkeley
at the University group,
of Vienna has continued
[85,86]. Jamie Warnerto studyandgraphene
co-workers usingat AC-TEM
Oxford have at theconducted
Universitya
of Vienna [85,86]. Jamie Warner and co-workers at Oxford have conducted
comprehensive analysis of defects in single-layer and bilayer graphene [87–90], while the Manchester a comprehensive analysis of
defects in single-layer and bilayer graphene [87–90], while the Manchester
group [91] and the SuperSTEM team at Daresbury [92] have studied a range of 2-dimensional group [91] and the SuperSTEM
team at Daresbury
materials [92] have studied
and heterostructures, a range
as well of 2-dimensional
as graphene. materials andforms
Three-dimensional heterostructures,
of grapheneas havewellalso
as
graphene. Three-dimensional forms of graphene have also been
been investigated by the present author in partnership with the Manchester and SuperSTEM investigated by the present author in
partnership
microscopists with[93].
the Joerg
Manchester
Jinschek andofSuperSTEM
the FEI Companymicroscopists [93]. Joerg Jinschek
and co-workers used the of technique
the FEI Company of exit-
and
wave co-workers
reconstructionused the to technique of exit-wave
obtain extremely high reconstruction
quality imagestoofobtain extremely
graphene usinghigh quality images
an AC-TEM of
at 80 kV
graphene using an AC-TEM at 80 kV [94]. Exit-wave reconstruction involves
[94]. Exit-wave reconstruction involves extracting the wave function at the exit surface of the extracting the wave function
at the exit surface
specimen, of the specimen,
with aberrations and with aberrations
incoherence dueandtoincoherence
the imaging due to theremoved.
optics imaging optics removed.
Jinschek et al.
Jinschek et al. applied this method to a through focal series of micrographs
applied this method to a through focal series of micrographs of a region containing single-layer and of a region containing
single-layer
bilayer graphene and bilayer graphene
to produce the to produce
superb imagethe shown
superb in image
Figure shown
12. in Figure 12.

Figure 12. (a) Exit wave function (EW) reconstruction TEM image of single and bilayer graphene sheets;
Figure 12. (a) Exit wave function (EW) reconstruction TEM image of single and bilayer graphene
(b,c) Higher magnification colourised images from parts of single and bilayer regions. Reproduced
sheets; (b,c) Higher magnification colourised images from parts of single and bilayer regions.
with permission from [94]. Elsevier, 2011.
Reproduced with permission from [94]. Elsevier, 2011.

IfIfimaging
imaginggraphene
graphene using
usingaberration-corrected
aberration-corrected TEM
TEM presents
presents aa challenge
challenge [95],
[95],then
thenobtaining
obtaining
AC-TEM
AC-TEM images of diamond is even more demanding. Whereas graphene is naturally justone
images of diamond is even more demanding. Whereas graphene is naturally just oneatomic
atomic
layer thick, bulk diamond has to be thinned down to a thickness of less than 50 nm in order to obtain
layer thick, bulk diamond has to be thinned down to a thickness of less than 50 nm in order to obtain
interpretable images, and this is a non-trivial task. One of the few AC-TEM studies of bulk natural
C 2018, 4, 4 12 of 17

C 2018, 4, 4 12 of 17
interpretable images, and this is a non-trivial task. One of the few AC-TEM studies of bulk natural
diamond was
diamond carried out
was carried out by
by Iain
Iain Godfrey
Godfrey and
and Ursel
Ursel Bangert
Bangert atat Manchester
Manchester [96].
[96]. Aberration-corrected
Aberration-corrected
STEM imaging
STEM imaging and
and EELS
EELS were
were used
used totoinvestigate
investigatethe
thefactors
factorsthat
thatdetermine
determinetheir
theircolour,
colour,with
witha
a particular focus on vacancy clusters. Unlike natural diamond, synthetic diamond
particular focus on vacancy clusters. Unlike natural diamond, synthetic diamond produced by produced by
chemical vapor
chemical vapor deposition
deposition (CVD)
(CVD) is
is relatively
relatively amenable
amenable toto TEM
TEM study.
study. It
It can
can be
be deposited
deposited asas aa thin
thin
film and then further thinned using ion milling to produce electron-transparent specimens.
film and then further thinned using ion milling to produce electron-transparent specimens. In 2006, In 2006,
an international
an group led
international group led by
by Rolf
Rolf Erni
Erni used
used an
an aberration-corrected
aberration-corrected STEMSTEM to to resolve
resolve the
the 0.089
0.089 nmnm
“dumbbell” distance in the <110> zone axis orientation of CVD diamond [97].
“dumbbell” distance in the <110> zone axis orientation of CVD diamond [97]. A Japanese group, A Japanese group,
including Suenaga,
including Suenaga, Hidetaka
Hidetaka Sawada,
Sawada, andand Kunio
Kunio Takayanagi,
Takayanagi, recorded
recorded aa similar
similar image,
image, shown
shown in in
Figure 13, using an aberration-corrected TEM in 2013 [98]. These images provide
Figure 13, using an aberration-corrected TEM in 2013 [98]. These images provide a vivid a vivid demonstration
of the resolvingof
demonstration power of this new
the resolving generation
power of microscopes.
of this new generation of microscopes.

Figure 13. Aberration corrected TEM image of diamond projected along <110>. (a) Magnified image.
Figure 13. Aberration corrected TEM image of diamond projected along <110>. (a) Magnified image.
(b) Full image. An intensity profile is shown at upper right and a simulated image is shown as an
(b) Full image. An intensity profile is shown at upper right and a simulated image is shown as an
insert in (a). From work by Hosokawa et al. Reproduced with permission from [98]. Oxford University
insert in (a). From work by Hosokawa et al. Reproduced with permission from [98]. Oxford University
Press, 2013.
Press, 2013.

4. Discussion
4. Discussion
In the past 70 years, transmission electron microscopy of carbon has advanced from low resolution
In the past 70 years, transmission electron microscopy of carbon has advanced from low resolution
imaging of carbon black particles to recording images and spectra from individual atoms. These
imaging of carbon black particles to recording images and spectra from individual atoms. These
amazing advances have been made possible by the skill and dedication of many outstanding
amazing advances have been made possible by the skill and dedication of many outstanding scientists.
scientists. Some of the leading figures in the field are shown in Figure 14. Trevor Evans of Reading
Some of the leading figures in the field are shown in Figure 14. Trevor Evans of Reading University
University was the first to study diamond by TEM, and his group was responsible for recording the
was the first to study diamond by TEM, and his group was responsible for recording the first images
first images of platelets and voidites. Reading remained at the forefront of TEM studies of diamond
of platelets and voidites. Reading remained at the forefront of TEM studies of diamond for many
for many years, together with workers from Oxford, including Peter Hirsch, John Barry, John Bruley,
years, together with workers from Oxford, including Peter Hirsch, John Barry, John Bruley, and John
and John Hutchison, and Mick Brown and colleagues from Cambridge. These researchers pushed
Hutchison, and Mick Brown and colleagues from Cambridge. These researchers pushed against the
against the limits of the technology available at the time to eventually establish the true nature of the
limits of the technology available at the time to eventually establish the true nature of the defects that
defects that had been first observed at Reading in the early 1960s.
had been first observed at Reading in the early 1960s.
Robert Heidenreich of Bell Labs was a pioneer in the application of TEM to metals, and made a
very significant contribution to the study of carbon by recording the first lattice images of graphitized
carbon black in 1968. In Heidenreich’s work, the carbon black was intended to be a “test object” for
high resolution TEM, but the demonstration that graphite planes could be directly imaged opened
the way for a massive expansion of TEM studies of sp2 carbon in all its forms. This led to many
C 2018, 4, 4 13 of 17

Robert Heidenreich of Bell Labs was a pioneer in the application of TEM to metals, and made
a very significant contribution to the study of carbon by recording the first lattice images of graphitized
carbon black in 1968. In Heidenreich’s work, the carbon black was intended to be a “test object” for
high resolution TEM, but the demonstration that graphite planes could be directly imaged opened the
C 2018, 4, 4 13 of 17
way for a massive expansion of TEM studies of sp2 carbon in all its forms. This led to many important
advances in ouradvances
important understanding of graphite, glassy
in our understanding carbon,
of graphite, carbon
glassy black,
carbon, carbon
carbon black,fibres,
carbonand catalytically
fibres, and
grown carbon filaments.
catalytically grown carbon filaments.

Figure 14. Some

Figure of the
14. Some pioneers
of the ofofthe
pioneers thestudy
study of carbon
carbonby byTEM.
TEM. Clockwise
Clockwise from
from top top
left: left:
TrevorTrevor Evans,
Evans,
Robert Heidenreich,
Robert Kazu
Heidenreich, Suenaga,
Kazu Suenaga, and
andSumio
SumioIijima.
Iijima.

Sumio Iijima of the NEC Corporation is best known for the discovery of a completely new form
Sumio Iijima of the NEC Corporation is best known for the discovery of a completely new form
of carbon filaments—fullerene-related carbon nanotubes—in 1991, but he had been a leading figure
of carbon filaments—fullerene-related
in electron microscopy since the earlycarbon nanotubes—in
1970s, making important1991, but he had
contributions been
to the a leading
study figure in
of complex
electron microscopy since the early 1970s, making important contributions to the study
oxides and ultra-fine metal particles. Since 1991, he has concentrated most of his research effort on of complex
oxides and ultra-fine
carbon nanotubes,metal
carbonparticles.
nanohorns, Since
and 1991, he has
graphene, andconcentrated
continues to most
publish ofpapers
his research
on TEM effort
of on
carbon nanotubes,
carbon carbon
to this day. nanohorns,
Kazu Suenaga and
of AIST in graphene,
Tsukuba, whoandhascontinues to publish
worked closely papers
with Iijima, onway
led the TEM of
in to
carbon thethis
application
day. Kazuof aberration-corrected
Suenaga of AIST in TEM to carbon,
Tsukuba, whorecording some closely
has worked of the first truly
with atomic
Iijima, led the
resolution images of carbon nanotubes and graphene. The development of these new
way in the application of aberration-corrected TEM to carbon, recording some of the first truly atomic super-high
resolution
resolution microscopes
images of carbonhas nanotubes
represented aand quantum leap inThe
graphene. carbon imaging and of
development fortuitously
these new coincided
super-high
with the discovery of graphene; much of what we now know about defect structures in graphene has
resolution microscopes has represented a quantum leap in carbon imaging and fortuitously coincided
been obtained by the application of AC-TEM. Carbon science has seen some extraordinary advances in
with recent
the discovery of graphene; much of what we now know about defect structures in graphene has
years. However the field develops in the future, it seems certain that TEM will continue to play a
been central
obtained by
role. the application of AC-TEM. Carbon science has seen some extraordinary advances in
recent years. However the field develops in the future, it seems certain that TEM will continue to play
Acknowledgments:
a central role. I am grateful to Chris Ewels, Malcolm Heggie, Fredrik Hage, Jon Goss, Kazu Suenaga, and
Hidetaka Sawada for helpful discussions and comments. Special thanks go to John Barry for helping to guide me
through the complexities
Acknowledgments: of defects
I am grateful in diamond.
to Chris Ewels, Malcolm Heggie, Fredrik Hage, Jon Goss, Kazu Suenaga, and
Hidetaka Sawada for helpful discussions and comments. Special thanks go to John Barry for helping to guide me
Conflicts of Interest: The author declares no conflict of interest.
through the complexities of defects in diamond.
Conflicts of Interest: The author declares no conflict of interest.
References
1. Ruska, E.; Knoll, M. Das Elektronenmikroskop. Z. Phys. 1932, 78, 318–339.
References
2. Scherzer, O. Über einige Fehler von Elektronenlinsen. Z. Phys. 1936, 101, 593–603.
1. 3. Heidenreich,
Ruska, R.D.Das
E.; Knoll, M. Electron microscope and diffraction
Elektronenmikroskop. Z. Phys. study
1932, of
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