Efficient 3.

3ym light emitting diodes for detecting methane gas at room temperature
M . K . Parry and A. Krier

1500

16ps/divisron

156 155 wavelength, pm

Indexing terms: Light emitting diodes, Gas sensors, Optical sensors

In,,,Ga,,,As light emitting diodes were grown on p-type InAs substrates by liquid phase epitaxy (LPE). These devices exhibit efficient infrared emission at 3 . 3 and ~ can be used to fabricate infrared methane gas sensors for the cost-effective detection and monitoring of methane gas in various applications. High quality In, .Ga,As is a promising material for the fabrication of infrared light-emitting diodes operating over a wide range of wavelengths. In particular, devices which emit near the fundamental hydrocarbon absorption band at 3 . 3 2 are ~ of special interest for the detection of combustible gases such as methane. There have been numerous investigations of both MBE and MOVPE growth of strained, gallium-rich InGaAs on GaAs substrates for high speed electronic devices such as MODFETs [ I , 21, and many reports of lattice matched In,,,G+4,As epitaxy onto InP for 1 . 5 5 ~ lasers, LEDs and detectors [3-51. However, despite its technological importance for the fabrication of long wavelength optoelectronic components, In-rich InGaAs has by comparison received very little attention. Consequently, there are as yet no reports of any useful 3 . 3 2 light ~ sources from either of these epitaxial growth techniques. The required In, .Ga& composition necessary for a 3 . 3 2 ~ emission wavelength is estimated to be x = 0.03 at 300K [6] and whereas the successful LPE growth of In-rich In,J3a,As ( x < 0.1) onto InAs substrates has been reported [7], difficulties were found with reproducibility and with indium melt inclusions formed at the InGaAsiInAs heterojunction interface resulting from melt-substrate instability [SI. A further investigation of the compositional dependence of the surface morphology and the formation of the inclusions with the gallium fraction in the growth melt has shown that reducing the gallium content of the melt resulted in fewer inclusions and epitaxial layers of constant solid composition [9]. This has recently led to the fabrication of prototype pn-junction light sources operating in the infrared with room temperature electroluminescence emission over a wide wavelength range of 2.613 . 8 2 [IO]. ~
2 5

1 6ps/division

Fig. 4 Demultiplexed characteristics: demultip1e.ws signal, and residual

control pulse a demultiplexed (switched) signal from CW signal b corresponding spectrum c residual control pulse waveform at 1 . 5 2 5 ~

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0 IEE 19941
Electronics Letters Online No: 19941352

26 September 1994

E. Yamada, K. Suzuki and M. Nakazawa ( N T T Access Network Systems Laboratories, Optical Trunsmission Line Laboratory, Tokai, Ibaraki- Ken 31 9-11. Japan)

References
DIGIOVANNI. D J , R A , and WECHT, K.W : 64Gbls all-optical demultiplexing with the nonlinear optical-loop mirror, IEEE Photonics Technol. Lett., 1992, 4, pp. 64&647 2 KAWANISHI. S , MORIOKA, T., KAMATANI. 0 , TAKARA, H , and SARUWATARI, M : IOOGbitis, 200km Optical transmission experiment using extremely low jitter PLL timing extraction and all-optical demultiplexing based on polarisation insensitive fourwave mixing, Electron. Lett., 1994, 30, pp. 800-801 3 GLESK, I , SOKOLOFF. J P, and PRUCNAL. P R : Demonstration Of alloptical demultiplexing of TDM data at 250 Gbitis, Electron. L e t t , 1994, 30, pp. 339-340 N J , and WOOD, D : Nonlinear-optical loop mirror, Opt 4 DORAN. Lett., 1988, 13, pp. 56-58 5 FERMANN. M E , HABERL. F , HOFER, M , and HOCHREITER, H . : Nonlinear amplifying loop mirror, Opt Lett., 1990, 15, pp. 752754 6 WHITAKER. N.A,AVRAMOPOULOS. H , FRENCH, P M w , GABRIEL. M.c., LAMARCHE, R E, GIOVANNI, D J DI, and PRESBY, H M : All-optical arbitrary demultiplexing at 2.5Gbitis with tolerance to timing jitter, Opt. Lett., 1991, 16, pp. 1838-1840 7 PATRICK, D M , ELLIS. A D , and SPIRIT, D M : Bit-rate flexible alloptical demultiplexing using a nonlinear optical loop mirror, Electron. Lett., 1993, 29, pp. 702-703 8 NAKALAWA. M , SUZUKI, K , and KIMURA. Y : Transform-limited pulse generation in the gigahertz region from a gain-switched distrihuted-feedback laser diode using spectral windowing, Opt Lett., 1990, 15, pp. 715-717 9 NAKAZAWA. M , KUROKAWA. K , KUBOTA. H., and YAMADA, E : Observation of the trapping of an optical soliton by adiabatic gain narrowing and Its escape, Phys. Rev. L e t t , 1990, 65, pp. 18811884 10 GORDON, I P : Theory of the soliton self-frequency shift, Opt. Lett., 1986, 11, pp. 662-664

ANDREKSON, P A ,

OLSSON, N A ,

SIMPSON, I.R.,

MORTON, P.A., TANBUN-EK, T ,

LOGAN,

30

3.5

4Q

Fig. 1 Typical room temperature electroluminescence emission spectrum of In, ,,Ga,,,As light emitting diode (200mA peak pulse drive current, 15% duty cycle)

The fundamental methane absorption spectrum 1s included for comparison [ I31 In the present work we demonstrate efficient, light emitting diodes at 3 . 3 operating ~ at room temperature. The diodes were grown by LPE using a horizontal, multiwell sliding graphite boat, in a Pd-diffused hydrogen atmosphere, using the procedures described previously elsewhere [I I]. The growth melts were prepared using 6Ws pure In and Ga and undoped polycrystalline InAs. The epitaxial layers were grown onto (100) oriented, p-type (zinc-doped at I0*/cm) InAs substrates obtained from MCP

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Wafer Technology Ltd. The melt composition necessary to grow the In,,,,Ga,,,,,As solid layers was determined by the systematic adjustment of the gallium fraction added to the melt while maintaining a constant InAsiIn weight fraction. Subsequent photoluminescence, energy dispersive and double crystal x-ray analysis confirmcd a final solid composition of In,,,,Ga,,,,,As as required. with a lattice mismatch of -0.02'%, (G2005ppm). The gallium mole fraction in the melt used t o grow these layers was X,, = 0.00179 (P,,, = 0.94253). Epitaxial growth at a temperature of 597.5"C with a cooling rate of O.?"C/min resulted in an average epitaxial layer thickness of 1 7 p after 5 min. The In,,,.Ga,,,As LED structures employed here comprised three epitaxial layers. The first ti-type layer (Te-doped) was 2 0 p thick and acts as a buffer layer to reduce the misfit dislocation density in the undoped active layer [12]. T h e undoped and top p type (Mn-doped) layers were both typically 4 p thick. T h e material was processed by mesa etching into I m m diameter surface light-emitting diodes using conventional phutolithographic techniques.

Fig. 2, at lo\\ voltage (< 0.09V) the ideality factor was typically I .9. consistent with generation-recombination current being the dominant current transport mechanism (141 ;ind the saturation current was typically 3.5 x I O hA/cm'. At higher applied voltages (> 0.09V) the ideality factor increases t o 4.1 due t o the diode series resistance of 0.24Q and 0.26R at 77 and 300K, respectively. The total light output power a n d efficiency against peak pulse drive current is sh0u.n for a typical In,,,Ga,,,,,As diode a t 300K in Fig. 3. These measurements were performed using a calibrated integrating sphere and 77K indium antimonide photodiode. We obtained rooni temperature external power efficiencies in the even though a saturation of the electroluminesrange 0.1 - 0.15'%1 cence emission intensity with increasing drive current was evident as a result of Joule heating effects due to the diode series resistance.

In conclusion, we have demonstrated that by using liquid phase epitaxy it is possible t o grow high quality indium-rich layers of thc ternary alloy InGaAs. Furthermore, this material can be used to ~ high fabricate light emitting diodes which operate at 3 . 3 with efficiency a n d are suitable as the key components in an infrared methane gas sensor.
Acknowledgment: The authors would like to thank EEV Ltd. and

EPSRC for supporting this work. 0 IEE 1994

Elertronim Letters Online No: IYY41360

7 Octohrr 1994

M. K. Parry and A. Krier (Applied Phvsics Division, I.uncu.str, University. Lancaster L A 1 4 YB, United Kingdom)

References
1
UEKGEK. P., and CHANl;. K : 'Role of strain and growth conditions on the growth front profile of In,Ga, ,As on GaAs during the pseudomorphic growth regime', Appl. P h j s Lett.. 1988, 53. pp. 684686
KALIULESCU. D , and SC'HAPF. w : 'Influence of substrate temperature and InAs mole fraction on the incorporation of indium during molecular-beam epitaxial growth of InGdAs single quantum wells on GaAs'. J . Vac. Sri. Techno/.. 1989, B7. pp. I I I I 1 5 AKIBA. 5 , and S A K A I . K : 'ln,,,,Ga,,,7As/ln, ,Ga,As,P, I double heterostructure lasers with emission wavelength of I .67m at room temperature', Jpn. J . Appl. Phys.. 1978. 17. pp. 1899~ 1900 PEARSALI., T , and M I L L E R . B : 'Efficient lattice-matched douhleheterostructure LED's at 1 . 1 from ~ Ga,ln, ,As,P, ,'. Appl. Phys. Lett.. 1976, 28, pp. 499-501 B A C H M A N S . K., and SHAY. J.: 'An InGaAs detector for the I.@ 1 . 7 wavelength ~ range'. Appl. Phys. Lett., 1978. 32. pp. 446 448 M A D E l . U h t i . 0. (Ed.): 'Data science and technology' (Springer, Bcrlin. 1978) GERKITSF.N. H.: 'Use o f room temperature diodes in monitoring specific gases in air. particularly methane and carbon monoxide'. Final Report. US Department of Interior, Burcau of Mines, Contract No. 90101740, Grant No. G010740. NTlS No. PB-2459I2IAS. 1974 ASTLES. M., and IIOSSER. 0 : 'Substrate instabilic) during [he LPE growth of (Ga,In)As alloys on lnAs substrates', .I. Crystrii Growth. 1981, 54, pp. 485 492 MATVEBV. B , and PLIIROV. v.: 'Features of growth and luminescence properties of epitaxial heterojunction structures based on In, GaAs and InAs, ,P, l i < 0.2) solid solutions'. l x A k u d N u u k SSSR, Neorg. M u l m . 1986, 22. pp. 482486 ZOTO\'A. N.. and KARANIIASHFV, S.:'Optoelectronic sensors based on narrow band A'B' alloys'. SPIE-Chemical, Biological and Environmental Fiber Sensors 111, 1991. Vol. 1587, pp. 334~345 P A R R Y . M , and KK1tK.A: 'Liquid phase cpiraxial growth and photoluminescence of Mn-doped InGaAs with InAs-enriched composition', J. Crystal Growth, 1994, 139, pp. 23X 246 PARRY, M.. and KKIER. A.: 'InteIfdCe recombination and photoluminescence efficiency of thick (> 3 p n ) LPE InGaAs with InAs-enriched composition', submitted to Thin Solid Films 1994 ROTHMAN. L. and <?.\MACHE. K : 'The Hitran molecn~ardatabase: Editions of 1991 and 1992'. J. Quuntuni Rudiution Transfer. 1992. 48, pp. 469 -507 MOSS, T. (Ed.): 'Handbook on semiconductors'. Vol. 4,pp. 469 507
I

0 05

0 10
voltage ,V

0 15

020
2

Fig. 2 Ln I - V p l m . f the D C current-voltuge chumcrerirrics a1 300K for one of the light emitting diode.s

5
6 7
t

01 02 03 04 peak pulse diode current.A Fig. 3 7btul power output and external p o w r efficient)' of one oJ the

80

--i
8

light rmirtin,y diodes against p r u k pulse drive current (IS'% duty cycle)

W power output 0 external power efficiency

The 300K electroluminesence emission spectrum from one of the In,,,Ga,,,,As LEDs is shown in Fig. I. The measurement was performed using a pulse current of 200mA a t a duty cycle of 15%. T h e diode emission, with a peak wavelength of 3 . 2 8 (~ FWHM = 432nm). corresponds very well t o the methane absorption spectrum at 300K [13]. The lower energy side of the spectrum has the shape of the conduction band density of states, while the high energy side is determined by the thermal distribution. The forward current-voltage characteristics a t 300K closely follow the classical exponential behaviour consistent with injection over a potential barrier (-0.4eV). The reverse breakdown voltage decreases with increasing temperature and the diode leakage current increases (i.e. a negative temperature coefficient for breakdown). Such behaviour is typical of narrow gap semiconductors. As shown in

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