Glass-ceramics for photonic applications: an example (Reference based optical characterization of glassceramic converter for high power white

LEDs)

Authors: A. Engela, M. Letza, T. Zachaua, E. Pawlowskia, K. Seneschal-Merza, T. Korba, D. Enselinga, B. Hoppea, U. Peucherta, J.S. Haydenb Presented by: U. Fotheringhama AG, Hattenbergstr. 10, 55014 Mainz, Germany bSCHOTT North America, RDD, 400 York Avenue, Duryea, PA 18642 USA
aSCHOTT

Outline motivation glass ceramic at Schott (definition of glass ceramics) glass ceramic converter materials description of fluorescence measurements together with the corresponding scattering regimes used metrology for lifetime determination lifetime measurements on our glass ceramics conclusion

Standard White LED light generation: conversion using YAG:Ce

Goal: development of converter materials for HB-WLEDs

blue LED + yellow converter = white LED

wavelength in nm

Motivation
Usually this phosphor is applied as a powder which is embedded in a polymer or silicone matrix. This solution has besides some processing steps two major drawbacks. 1) large refractive index of n=1.836 (YAG crystals) are embedded in a material with a much lower refractive index in the order of 1.45 1.55. Large difference in refractive index leads to high amount of scattering light decreasing by strongly reducing the size of the crystallites recommended leading to the development of nano-YAG. 2) Organics materials involved suffer from thermal and radiation stabilty - strong radiation - high temperature and - non negleglible part of UV radiation Therefore glass ceramics with small n as solely solid state solutions for converter materials can be promising candidates for color conversion.

GCs property combination due to interaction of synthesis, process & texture

Properties
(mechanical, physical, chemical)

Li2O Na2O Al2O3 SiO2 TiO2 ZrO2 composition

texture

Ceramization

Green glass fabrication

processing

Glass ceramics offers promising product opportunities

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Products made from glass ceramics exhibit...
high optical transparency high temperature resistance high temperature shock resistance adjustable CTE high chemical durability ...

... yielding low-expansion SCHOTT products for different application fields

Aerospace Home appliances
ROBAX ZERODUR

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CERAN

Lithography

Projection

ZERODUR

The Core: Crystallization and Crystal Phases ( MgO-Al2O3-SiO2-GK)

type and amount determines:
180

CTE30-300 ~6,5 ppm/K

DTA [@ 5 Kmin ; arb. un.]

mechanical properties 170 thermal expansion thermal stability 160 chemical stability toughness 150 transparency
E / GPa
140

CTE30-300 ~6 ppm/K

130

CTE30-300 ~5 ppm/K
500 600 700 800 900 1000 1100 1200 1300 1400 1500

T / C

spinel sapphirine cordierite

-1

Glass ceramics from the Y2O3-Al2O3-SiO2-system

Yttriumpyrosilicate (Keiviite)

Mullite

Yttrium Aluminium Garnet

We realize a pure YAG phase in our YAS-glass ceramic

electron microscopy shows crystallites and residual glass example:

X-ray diffraction proves pure YAG as crystalline phase!! samples turn yellow

Light conversion on 0.1-0.5mm thick samples possible:

Remission (diffuse reflection): YAG:Ce phosphor and YAG:Ce glass ceramics

glass ceramic shows a remission at 460 nm which is comparable to Ce:YAG powder On the other hand the remission spectra that the spectral profile of the glass ceramic shows less structuring in comparison to the phosphor. This may be explained by the different scattering regime of the glass ceramic together with the vicinity of the band-gap of the host glass.
3% YAC:Ce in Silicone
1.0 0.9 0.8 0.7

phosphor powder

Schott 5 0.328 mm

YAG:Ce powder YAG:Ce in Silicone

Remission

0.6 0.5 0.4 0.3 0.2 0.1 0.0 250

Schott glass ceramic

300

350

400

450

500

550

600

650

700

750

800

850

Wavelength (nm)

Excitation & emission spectra of YAG:Ce phosphor & glass ceramics

We observe the expected spectral absorption and emission profiles. For the phosphor we find absorption and excitation for maximum at 350 and 450 nm, whereas for the glass ceramics we see mainly the 450 nm absorption. This reduction of the 350 nm excitation is determined by the bandgap absorption of the host glass system.
4500000 1% YAG:Ce in Silicone emissio em 460 nm 4000000 3500000 3000000 1% YAG:Ce in Silicone emissio ex 545 nm Schott 5 em 460 nm Schott 5 ex 545 nm

Intensity in cps

2500000 2000000 1500000 1000000 500000 0 290 390 490 590 690 790

Wavelength in nm

FLUOLOG 3 with IBH lifetime module with Time correlated single photon counting TCSPC

The lifetime l of the Ce3+ fluorescence level is completely independent on the scattering regime !

id

NR

l : measured lifetime, id : lifetime of YAG:Ce in a perfect single crystal, approximately 67ns NR : originates from non radiative processes, which are e.g. coupling to phonon modes or coupling to impurities in the material.

Lifetime measures internal quantum efficiency !

FLUOLOG 3 with lifetime module

detection performed using identical double monochromators of the FLUOLOG 3. Synchronization of pulsed ignition and detection performed via a controller, which determines the timing of excitation and that of emitted photons and calculates the respective time of delay. decay time of a fluorescent state is defined as the time interval after which the initial intensity has decreased to 27 % (= 1/e part).

Decay curve and evaluation of YAG:Ce glass ceramics.

periodic excitation by the LEDs can reconstruct the single decay profile from single photon events collected over many cycles. reference for the timing: corresponding excitation pulse. The method is based on the repetitive precise timing registration of single photons.

Cts

fluorescence signal scattering

Std. Dev.

Channels (1 Ch = 0.28 ns)

Auto-corr.

fitting accuracy

Decay curve of CaF2:Pb for the emission of 540 nm

Testing procedure for the fluorescence decay measurement using a doped CaF2:Pb crystal. The sample itself is transparent in the visible range.
3500

3000

CaF2:Pb; em: 540 nm ExpDec fit

2500

2000

Cts

1500

1000

500

0 0 10 20 30 40 50 60 70 80

Delay in ns

Decay curve of CaF2:Pb for the emission of 540 nm

Comparative measurements using different diagnostics and excitation sources at Piqoquant, PTI and Schott mono-exponential decay with a decay time between 24.3 0.3 ns and 21.60 0.49 ns respectively. differences due to non-identical set of evaluated data for mono-exponential fitting

Decay time for 540 nm [ns]

25 24 23 22 21 20 19 1 2 3 Lab 4 5 min max

Lifetime evaluation using mono exponential fitting procedures

A mono-exponential fit is very sufficient to determine the lifetime of the observed emission The shape of the decay curves is very similar, but the intensity is different between the phosphor and the glass ceramic material. This may be explained by the different absorption mechanism, but nevertheless the observed samples show the same decay characteristics.

Lifetime dependency versus temperature

The temperature dependency shows no significant changes within the accuracy In order to check how temperature dependent effects occur, as already reported for different types of phosphors, we have to improve the accuracy of our measurements for these types of material.
Schott 5 70 Decay time in ns 65 60 55 50 45 -50 0 20 60 100 130 150 Temperature in C Schott 1 Schott 1 repro 3 % in Silicone

Single crystal lifetime at RT 67 +/- 6 ns

E.Zych et al. J. Lum. 75, 193 (1997)

60 - 65 ns
E. Mihokova et al. J. Lum. (2006)

Conclusion Lifetime measurements

The lifetime measurement of the Ce3+ fluorescence in our glass ceramic has been performed for the first time. Accurate lifetime measurements in our glass ceramic show a lifetime of 62 +/- 6 ns and suggest that our material is at least comparable to existing YAG:Ce phosphors (67 +/- 5 ns) with respect to internal conversion efficiency. We believe to reach an accuracy below 10 %. In the nearest future round robin tests have to be performed in order to check the consistency of the fitting procedures. Next steps will be further temperature dependent measurements in order to prove the observed shifts of the life time

Conclusion
A glass ceramic material shows large potential as a converter material for blue-white light conversion in a white LED. Our glass ceramic is a moderate scattering, translucent material. it allows freedom of design to adjust the scattering level it offers a challenging regime for measuring and quantifying fluorescence. As a first step we showed fluorescence as well as excitation spectra and measurements of the life time for the Ce3+ fluorescence. We conclude from lifetime measurements that our material has practically no additional channels for non radiative decay. There is no principle reason that this glass ceramic material will not reach best conversion efficencies know today from phosphor powders.