1040

IEEE JOURNAL ON SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 6, NO. 6, NOVEMBER/DECEMBER 2000

IIIV Semiconductor Heterojunction Devices Grown by Metalorganic Chemical Vapor Deposition

Russell D. Dupuis, Fellow, IEEE
Invited Paper

AbstractSeveral important early developments in the metalorganic chemical vapor deposition technology relate to the demonstration of high-performance AlGaAsGaAs injection lasers and solar cells in the late 1970s. It has been nearly 24 years since the first semiconductor injection lasers grown by metalorganic chemical vapor deposition (MOCVD) were made and nearly 22 years since the first continuous-wave quantum-well injection lasers were made by this process. In this past 20-odd years, MOCVD has been developed for the production of AlGaAs, InAlGaP, InGaAsP, InAlGaN, and a variety of other compound semiconductor materials. It is now the dominant technology for the production of light-emitting diodes, injection lasers, solar cells, photodetectors, and heterojunction bipolar transistors and a variety of other solid-state devices. This paper will review some of the early developments in this technology. Index TermsAluminum gallium arsenide, heterojunction lasers, metalorganic chemical vapor deposition, quantum-well lasers.

I. INTRODUCTION HE METALORGANIC chemical vapor deposition (MOCVD) technology for the growth of IIIV compound semiconductors developed quickly over the past twenty years to become the dominant epitaxial materials technology for both research and production. Because of the improvement in the material quality produced by MOCVD, many important IIIV devices have become commercially viable. The MOCVD epitaxial growth technology was first reported in the scientific literature in 1968 by Manasevit [1],1 although similar processes and experimental results were previously described in the patent literature by other workers, e.g., Scott et al. [2], Miederer et al. [3], and Ruehrwein [4][6], prior to 1967. Manasevit was primarily interested technologies for the heteroepitaxial growth of IIIVs on insulating substrates, the analog of the silicon-on-insulator (SOI) and silicon-on-sapphire

Manuscript received July 17, 2000. The work described here that was performed by the author at Rockwell International was partially sponsored by Rockwells Internal Research and Development funding and by the Energy Research and Development Administration (ERDA) (which later became part of the Department of Energy). AT&T Bell Laboratories sponsored the work performed at Bell Labs. The author is with The University of Texas at Austin, Microelectronics Research Center, Austin, TX 78758 USA (e-mail: dupuis@mail.utexas.edu). Publisher Item Identifier S 1077-260X(00)11610-7.
1In order to protect the North American Rockwell patent position, no details on the growth process are described in this paper.

(SOS) technology that he had developed earlier [7]. In fact, this first paper on MOCVD concerned the epitaxial growth of GaAs on insulators and the actual epitaxial process is not even mentioned [1]! While he and other workers studied the growth of IIIVs by this process in the early and middle 1970s, they were unable to demonstrate materials quality comparable to that of other IIIV epitaxial technologies such as liquid-phase epitaxy (LPE) and halogen- and hydride-based vapor-phase epitaxy (VPE) [8][11]. In 1977, Dupuis et al. reported the first AlGaAsGaAs high-efficiency solar cells grown by MOCVDthese were the first device-quality heterojunctions grown by MOCVD [7]. A short time later, Dupuis et al. reported room-temperature operation of high-quality AlGaAsGaAs double-heterostructure (DH) lasers with pulsed threshold current densities as low as those demonstrated for similar devices grown by liquid-phase epitaxy (LPE) [13], [14]. This announcement was followed by results showing CW operation of by the end of 1977 [15] and the operation of lasers with AlGaAs active regions in that same year [16]. These results firmly established the potential of the MOCVD process to produce high-quality Al-bearing layers from vapor-phase sources. This paper will review the early advancements in MOCVD technology and speculate on the future applications of this technology. Over the years since 1968, there have been several other names applied to this process, including: metal alkyl vapor phase epitaxy (MAVPE), metalorganic VPE (MOVPE), organometallic CVD (OMCVD), and organometallic VPE (OMVPE). However, Manasevit first used the term metalorganic because that was the common term applied to the metal alkyl compounds at this time and CVD because he felt that the process could be broadly applied to chemical vapor deposition of many different materials, including polycrystalline and amorphous filmsthe term vapor-phase epitaxy is a special case of the more general term CVD. Later, the term organometallic came to be applied to these specific compounds by the synthetic chemists studying these materials. II. EARLY MOCVD GROWTH OF COMPOUND SEMICONDUCTORS The growth of compound semiconductors using Column III metalorganic compounds and Column V hydrides begins in 1960 with the work of Didchenko et al. who explored the

1077260X/00$10.00 2000 IEEE

DUPUIS: IIIV SEMICONDUCTOR HETEROJUNCTION DEVICES GROWN BY MOCVD

1041

reactions of trimethylindium [In(CH ) , TMIn] and phosphine (PH ) at 300 C [17]. While these authors claimed that the adduct formed by this reaction decomposes sometimes explosively into InP and CH , they did not establish conclusively that the dark gray powder formed was in fact InP. In 1962, Harrison and Tompkins published a paper describing experiments in which they combined 1 : 1 mixtures of arsine (AsH ) and trimethylgallium [Ga(CH ) , TMGa] then heated the reaction products to 200 C to form a red compound that they claimed was GaAs [18]. Another early consideration concerning the growth of IIIV semiconductors by MOCVD was made by Dr. R. A. Ruehrwein of Monsanto who applied for patents in 1961 on many of the VPE processes for the growth of IIIVs, including the idea of using metalorganic Column III precursors in combination with Column V hydrides [4][6].2 In late December 1967, Manasevit submitted his first paper describing epitaxial growth of GaAs on insulating substrateshowever, the actual growth process was not mentioned [1]. This work was presumably performed without knowledge of the previous related patents and prior published results describing the bulk growth of semiconductors using metalorganic compounds.3 Manasevit did not describe the MOCVD growth process because he wanted to patent this inventionin fact, shortly after Manasevits first paper appeared, Rockwell filed a patent application on MOCVD, Ser. no. 705 213, on Feb. 13, 1968. However, this was denied because of the previous Ruehrwein patents [4][6]. The first detailed description of the MOCVD process was given in a later paper [19]. Somewhat ironically, Rockwell applied again for a patent on MOCVD in 1978 anticipating that the Monsanto patents were going to expirethey were granted a patent in 1983. This delay was fortunate for Rockwell because this patent covers the time period when MOCVD actually was making products with very large profits [20]!4 In 1997, the Rockwell patent was ruled invalid by a United States Federal Court [21]. Subsequently, it was reinstated upon appeal by Rockwell. It is interesting to note that, along with MOCVD, many important innovations in IIIV epitaxial growth technologies were first explored in the 19661967 time frame. For example, open tube hydride VPE growth of IIIVs was first reported by Tietjen and Amick in 1966 [22]. Liquid-phase epitaxial growth of AlGaAs was first reported in 1967 by Rupprecht et al. [23] and Arthur reported his first studies of the properties of Ga and As molecular beams in 1967 [24], which ultimately led to molecular beam epitaxial growth of GaAs by Cho in 1970. The first report in a scientific journal regarding devices fabricated from MOCVD-grown material was a 1969 paper by Waldner and Rouse, who fabricated GaAs FETs from material grown by Manasevit [25]. Over the next few years, Manasevit and co-workers explored the growth of IIIV, IIVI, and IVVI compounds by MOCVD [26][28]. Manasevits work concentrated on the growth of thin semiconductor films on various insulating oxide substrates including sapphire, spinel,
2These patents prevented Rockwell from patenting the MOCVD process in 1968. 3However, Tompkins paper is referenced in Manasevits first paper describing MOCVD [19]. 4This patent was still the subject of litigation as of July 2000.

beryllium oxides, etc. The reason for this focus was his interest in IIIVs on insulatorsthe analog of the Si-on-sapphire technology he pioneered earlier.5 Much of Manasevits work was proof-of-concept growth studies on insulators and the purity of the alkyl sources was still very far behind that of other precursors used for IIIV epitaxial growth. Furthermore, the MOCVD process is very sensitive to oxygen (more so than LPE and VPE), and the quality of the films is degraded when small oxygen leakss exist in the reactor system. Given the state of the art in reactor system design and construction in the early 1970s, this oxygen sensitivity created serious problems, especially for the growth of Al-containing alloys. These combined effects led to low carrier mobilities, high background impurity concentrations, poor surface morphologies, and generally low photoluminescence efficiencies compared to those achieved by other IIIV materials technologies. By the time Manasevits first paper appeared in 1968, many processes for the growth of IIIV epitaxial films were under active study and development. Holonyak was the first to investigate the epitaxial growth of IIIV compound semiconductors [29]. He used a closed ampoule process to grow GaAs, GaAsP, and GaP on a variety of substrates, also creating the first IIIV heterojunctions. Since the early 1960s and into the middle and late 1970s, other IIIV materials technologies dominated the research and production efforts worldwide, including: 1) vapor-phase epitaxy (VPE) using Column V halides (e.g., AsCl ) and Column III metals [30];6 2) VPE using Column V hydride sources (e.g., AsH ) and Column III trichlorides, e.g., GaCl [31];7 3) liquid-phase epitaxy (LPE) using Column III metal solutions (e.g., Ga melts with GaAs source material) [32];8 4) molecular-beam epitaxy (MBE) using pure elemental sources (e.g., Ga and As) [33]. Already in 1968, when Manasevits paper first appeared, the VPE and LPE technologies were proven for the growth of a variety of high-performance IIIV devices. By 1973, hydride VPE dominated the production of GaAsP light-emitting diodes (LEDs) and halide VPE dominated the production of high-purity GaAs for electronic devices. LPE was the dominant technology for many IIIV compounds, especially Al-containing devices, including AlGaAs LEDs, lasers, solar cells, and other heterojunction devices. By 1975, MBE was being actively researched by a few groups, particularly at Bell Labs [34] and IBM [35]. Consequently, there was not much interest in MOCVDit was viewed as just another IIIV materials technologyand the materials results seemed to be much worse than that achieved by the other IIIV epitaxial growth technologies.
5At this time, semi-insulating GaAs was prepared by doping the ingot with deep centers, e.g., Cr, to provide deep electron traps to make the material insulating. This process was unreliable in that the insulating behavior was not uniform within an ingot and also would change after thermal cycling. 6N. Holonyak, Jr., working at General Electric, initiated the closed-tube VPE process using iodine and chloride transport for the growth of IIIVs in 1960. Subsequently, others (R. A. Ruehrwien and F. V. Williams at Monsanto) expanded this into an open-tube process using chloride transport. This became the dominant form of halide VPE. See the paper From Transistors to Light Emitters, by N. Holonyak, Jr. in this issue. 7An early summary of hydride VPE appears in [31]. 8LPE growth of IIIVs was first described by R. Nelson (RCA Laboratories) in 1961 at the Solid State Device Conference (Stanford, CA). This work was published in [32].

1042

IEEE JOURNAL ON SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 6, NO. 6, NOVEMBER/DECEMBER 2000

In 1975, Seki and co-workers described the first high-quality GaAs films grown by MOCVD [36].9 These were homoepitaxial films on GaAs substrates grown using specially purified triethylgallium [Ga(C H ) , TEGa] and AsH . The electronic properties of these films were studied as a function of temperature and 300 K mobility values of cm /V s and a maximum mobility cm /V s for value of cm was measured at 77 K. These values were the highest reported to that date for MOCVD-grown GaAs and compared favorably to the values then obtained for high-purity GaAs grown by the more conventional AsCl GaH system. This was a remarkable result at the time and showed that if careful purification routes were used for the sources, the fundamental electronic properties of GaAs grown by MOCVD could be good enough for the demonstration of useful electronic devices. III. DEVELOPMENT OF MOCVD FOR INJECTION LASERS While these results clearly established the fundamentally sound MOCVD capabilities for the growth of device-quality GaAs for electronic devices, the growth of high-quality Al-containing films was still problematical This was an important issue that I began to study in 1975. In March 1975, I joined the Rockwell International Electronics Research Center (later part of the Electronics Operations) in Anaheim, CA, to study the electrical and optical properties of MOCVD-grown IIIV materials. I started work by setting up a photoluminescence system for IIIV materials characterization. For this purpose, I ordered a new Ar-ion laser, photomultiplier, picoammeter, etc. While waiting for this equipment to arrive, I spent a few weeks studying the electrical properties of GaAs/sapphire heteroepitaxial films grown by Manasevit and Simpson.10 I had previous experience with the solution growth of InGaP and the LPE growth of GaAs, AlGaAs, and AlGaAsP at UIUC. In addition, I had studied the LPE growth of N and Zn-O doped GaP LEDs at Texas Instruments. Furthermore, I also had some indirect knowledge of the VPE growth of GaAsP alloys from experiences gained during my Ph.D studies at UIUC, where I worked with VPE crystals grown at Monsanto. I realized that the MOCVD process could do something very uniqueit could provide a VAPOR PHASE source of Al! While I knew that the conventional forms of VPE could handle Ga, In, As, P, Sb, and N very well, the VPE processes could not easily be used to transport Al due to the reactivity of the pure element and its subchlorides [37].11 LPE could handle Al but was limited by the tyranny of the liquid-solid phase diagram, generally poor reproducibility, uniformity, and surface morphology, and, I knew, was very limited in the epitaxial wafer area that could be produced in one run. However, MOCVD was a process that ap9This work employed a specially purified TEGa source produced by Sumitomo Chemical Co., Ltd. Japan. 10William I. (Bill) Simpson was Manasevits technician and was responsible for reactor construction and maintenance, operation of the system, and materials characterization. 11Al chlorides attack quartz at temperatures typically used for VPE growth, forming alumina, consequently the VPE growth of Al-containing IIIVs was always compromised by oxygen and Si impurities as well as the catastrophic failure of the reactor tube.

peared to be scalable (like VPE) and able to grow a wide variety of IIIVsin fact, virtually all of themwith the special and important bonus of being able to provide Al to the surface during the growth of an epitaxial film (like LPE). This important capability intrigued me and was a prime reason why I decided to work on MOCVD growth as well as on characterization and device fabrication. This would produce a direct method to provide the quick feedback necessary to improve the materials quality necessary to make AlGaAsGaAs heterojunction devices. In order to have control of the materials I would be characterizing, I decided to build a reactor system myself to study MOCVD growth of device structures and heteroepitaxial and homoepitaxial IIIV films. I was very familiar with this grow and characterize mode of materials and device research, since during my M.S. and Ph.D. research in N. Holonyak, Jr.s, lab at the University of Illinois in Urbana-Champaign, we built much of our own growth apparatus, even to the point of wiring our own furnace elements.12 Consequently, I already had some experience in building crystal growth systems in Holonyaks lab. In addition, after leaving the U of I, I worked in the Optoelectronics Group of the Semiconductor Division of Texas Instruments, Inc., Dallas, TX. There I built a new large-scale LPE system capable of growth on three 2.0 in diameter wafersfor the growth of GaP : N green and GaP : ZnO red LEDs, providing me some additional industrial experience in the design and fabrication of semiconductor epitaxial growth systems. I modeled my first Rockwell MOCVD system on the existing design of Manasevits MOCVD reactor that Simpson had built, taking particular care in the reduction of dead space and the leak integrity of the gas panel. Almost all of the gas valves, Swagelok fittings, and Rotameter; type gas flow meters, as well as the rf generator, hydrogen purifier, vacuum pumps, and other components that I had to work with were used. However, I took special care with the cleanliness and the assembly of the components to ensure that the system was as clean and leak-tight as possible.13 I knew that this would be critically important in the handling and use of Al-conaining alkyl compounds. This system had a vertical quartz chamber with a rotating (at 1020 rpm) horizontal SiC-coated graphite susceptor 2.0 in in diameter and rf heating. It operated at atmospheric pressure and employed a specially designed vent-run gas manifold, which permitted the metalorganic source flows to be directed into a vent line or into the reactor, making the gas switching time very short. A photograph of me working with this system taken in October 1975 is shown in Fig. 1. A close-up of the reactor chamber and rf-heated susceptor is shown in Fig. 2. At this time, I only had TMGa and AsH sources mounted on the system. Later in 1975, I added trimethylaluminum [Al(CH ) , TMAl] and the doping sources H Se and diethylzinc [Zn(C H ) , DEZn)] so that I could grow n-type and p-type doped films and AlGaAs heterojunction devices. I grew a variety of p- and n-type epi12In Prof. N. Holonyak Jr.s lab at the U of I, we had hand-made heating elements for over 30 individual furnaces for the growth of InGaP crystals by a solution-growth technique and also an LPE system for growing AlGaAsGaAs laser structures. 13All of the 316 stainless steel tubing was solvent cleaned and passivated and etched with HF : HNO : H O and carefully dried using methanol. Furthermore, all valves were solvent cleaned ultrasonically and all of the Swagelok ferrules were Au-plated to prevent them from galling when assembled.

DUPUIS: IIIV SEMICONDUCTOR HETEROJUNCTION DEVICES GROWN BY MOCVD

1043

Fig. 1. Photograph of me with the first MOCVD reactor I built at Rockwell International in 1975. Photograph taken October 20, 1975.

temperature, metal alkyl molar flow rates, and dopant flows, etc., took several months and was complicated by the fact that I initially had to rely primarily upon 300 K and 77 K Hall-effect data and surface morphology examination by Nomarski optical microscopy since my PL system was not operational in the early phases of this work. However, by working out the growth conditions for the best morphology and mobilities, the PL was also pretty good as far as I could tell. I found that the III/V ratio and growth temperature were critically important parameters for the growth of the best AlGaAs. Since I had no PL standards to examine for comparison, all of this work was performed on a relative basis. Rockwell had a Physical Electronics PHI Auger electron spectroscopy system in a nearby building so I took a few samples over there to study the AlGaAsGaAs interface abruptness and the oxygen impurity concentrations in the AlGaAs films. By early 1976, I had moved on to growing heterojunction devicesI was particularly interested in semiconductor lasers, which I knew about from my graduate student days at the U of I. The first device structure I grew was a simple GaAs pn junction. After I processed the devices from the wafer, I discovered that the current versus voltage ( ) characteristics looked good on the curve tracerand the device responded to the microscope lightso I decided to grow a solar cell structure using a thin AlGaAs window layer on top. After working out the growth conditions for various As alloy compositions, I found the conditions for a Al Ga like that wide-bandgap alloy with Al composition used for similar LPE-grown solar cells. After I processed this wafer into simple solar cell devices, I took them outside the building to test the devices. Using a digital multimeter, I found a large photocurrent was generated under such one-sun Air Mass one or so illumination conditions.14 In addition to being the first MOCVD-grown device of its kind (to my knowledge), this result was interesting because the US Government was starting to fund alternative energy research under the auspices of the Energy Research and Development Administration (ERDA). Further, optimization of the growth and more detailed device testing led to my publication of the first paper on the MOCVD growth of solar cells [12]. These uncoated devices exhibited 1-sun Air Mass Zero (AM0solar flux conditions in space) short-circuit current densities of 24.5 mA/cm , open-circuit voltages of 0.955 V, fill factors of 0.70 and power conversion efficiencies as high as 12.8% which compared well with the record efficiencies reported for LPE-grown devices of 17.2% for antireflection-coated cells.15 Subsequently, my Group at Rockwell received a contract from ERDA for solar-cell research, including the MOCVD growth of GaAs solar cells on low-cost substrates, e.g., glass, Mo, and Mo/glass composites [38]. I began the AlGaAsGaAs solar
14The term Air Mass Zero denotes photon flux conditions identical to outer space in the near earth region due to illumination from the Sun. Air Mass One corresponds to the solar flux conditions at the surface of the earth at sea level on a clear, cloudless day when the Sun is at its zenith. Air Mass Two corresponds to a reduced solar flux corresponding to a hazy day. 15These values are uncorrected for contact area and reflections from the AlGaAs surface. I estimated that anti-reflection coatings would raise the efficiency by about 3035% to make the AM0 efficiency of these MOCVD cells as high as 17.28%.

Fig. 2. Photograph of the MOCVD reactor chamber with a large-area (0001) sapphire substrate loaded on the 2.0-in diameter. SiC-coated graphite susceptor. Photograph taken October 20, 1975.

taxial layers on GaAs : Cr semi-insulating substrates to determine the doping concentration versus dopant molar flows for GaAs and AlGaAs films using Hall-effect characterization. The work on the optimization of the growth rate, V/III ratio, growth

1044

IEEE JOURNAL ON SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 6, NO. 6, NOVEMBER/DECEMBER 2000

cell research at Rockwell-Anaheim in this program using this first MOCVD reactor. The MOCVD technology is now the dominant materials growth technique for all IIIV solar cells. In 1975 and 1976, a few groups reported the characteristics of MOCVD-grown GaAs films and AlGaAsGaAs heterostructures. For example, Andre and co-workers reported on the growth of p-type GaAs and AlGaAs films on GaAs substrates for photocathodes [39]. The electron diffusion lengths in various p-type GaAs layers were measured to be comparable to that of LPE-grown films. However, many defects were observed in the AlGaAs films and no electrical or optical properties of the AlGaAs films were given. In 1975, Sidney Bass reported that the highest 300 K electron mobility for cm /V s his MOCVD-grown n-type GaAs was [40]. Also, in 1976, Allenson and Bass reported the growth of GaAs photocathodes on GaAs substrates by MOCVD [41]. cm and Undoped layers were p-type with cm /V s. Intentionally doped p-type films with cm cm were obtained using DEZn as a dopant. No data on AlGaAs were presented. The electron diffusion length was comparable to LPE-grown films with similar hole concentrations. Also, in 1976, White et al. published a comparative study of deep traps in bulk GaAs and LPE-, chloride VPE-, and MOCVD-grown epitaxial GaAs films [42]. This work showed that the MOCVD-grown films had a larger variety of electron traps than the other materials although the absolute trap concentrations were not measured. My work in 1976 focused on MOCVD growth of AlGaAsGaAs solar cells and the study of doping in AlGaAs. In addition, the new funding provided by the ERDA solar-cell contract allowed me to construct a second MOCVD reactor with many new components, including new stainless-steel Nupro Model 4H bellows-sealed valves, Tylan; Model 260 electronic mass flow controllers, and special Hoke three-port, low-dead volume bellows-sealed switching valves with face-sealing fittings using metal gaskets. Furthermore, I designed and built an improved reactor control system using a 16-channel Tylan electronic sequencer. Finally, I designed and built a gas distribution system with the TMGa, TMAl, and DEZn metalorganic source bubblers attached to the low-volume valves to provide for rapid switching. The electronic sequencer contained an optical card reader and could be programmed with punched IBM cards to load a run recipe containing many steps into memory for later execution. Again, I was very concerned about the effects of oxygen on the growth of the AlGaAs films, and although most of the stainless-steel tube fittings were Swagelok, I used careful cleaning, assembly, and sealing techniques to realize the best possible leak integrity of the system.16 I also designed and built special all-welded 316 stainless steel metalorganic source cylinders using electron-beam welding so that the alkyls would stay as pure as possible while they were used. I transferred commercially supplied alkyls into these vessels using a vacuum transfer procedure. To my knowledge, these are the first high-purity all-welded metalorganic source
16I did not have access to a conventional He mass-spectrometer leak detector, however (we did not have enough money to buy one), so I employed a rate of pressure rise test using a Hg diffusion pump and a thermocouple vacuum gauge to evaluate the system integrity.

Fig. 3. Photograph of the second MOCVD reactor I built at Rockwell in 1976. This system is computer controlled and contains a more advanced low-dead-volume gas-switching manifold. Photograph taken January 10, 1977.

cylinders ever made. A photograph of my more advanced second MOCVD reactor is shown in Fig. 3. At this time, there was no commercial vendor of MOCVD reactors so everyone had a different type of system because they were all built by individual researchersevery reactor was unique. I believe that, at the time this second reactor was completed (late 1976), this was the most advanced reactor being used for MOCVD growth. By the end of 1976, this reactor was fully operational and I started to work on AlGaAsGaAs solar cells to compare with those created with my other first reactor. Don Yingling17 was the primary operator of that first system, while I was the sole user of the new system. From the 300K PL that I measured using AlGaAsGaAsAlGaAs double-heterostructure (DH) standard samples, it was clear that this new MOCVD system was performing better. The uniformity of the deposition was readily optimized using AlGaAs films with grown on sapphire substrates. The optical interference of these wide-bandgap films with the underlying Al O substrate made it easy to determine how uniform they were. A color film grown photograph of a highly uniform AlGaAs on a 1.5-in diameter Al O substrate is shown in Fig. 4.18 In the study of AlGaAs for solar cells, I grew films with Al alloy to . I grew my first pure compositions from AlAs films accidentally when the TMGa source ran out during an AlGaAs run.
17Don Yingling was a technician working on LPE growth of GaP LEDs when he and I met at Texas Instruments in Dallas, TX in 1973. I hired him in 1976 to come to Rockwell to work on the solar-cell program and he operated the first MOCVD reactor while I built and operated the second one. Later, he moved to Xerox Palo Alto Research Center to build and operate an MOCVD reactor and to work on lasers with Dr. Robert D. Burnham and Dr. Donald R. Scifres. A lot of the features of my second reactor were used in the Xerox system. Subsequently the Xerox MOCVD reactor was used to grow laser material for the start-up of Spectra Diode Laboratories (now SDL Inc.). 18The AlGaAs alloy compositions were determined by a combination of 300K PL (for direct bandgap alloys), absorption measurements (for indirect alloys), and X-ray rocking curves for films grown on GaAs substrates.

DUPUIS: IIIV SEMICONDUCTOR HETEROJUNCTION DEVICES GROWN BY MOCVD

1045

However, the AlAs films rapidly degraded when exposed to air so I did not pursue this composition futher. However, As films with were very stable and I used Al Ga this alloy composition in some of the solar cell structures that I grew. I was also interested in trying to demonstrate an injection laser using the MOCVD process so I started to work on lasers grown in this reactor. Since I had made many injection lasers during my Ph.D. research in N. Holonyak, Jr.s, lab at the University of Illinois, I had a great deal of experience with lapping, metallizing, cleaving, and testing such devices. After growing the wafers, I processed them into laser bars for electrical and optical testing. I was successful in demonstrating 300 K pulsed laser operation with low threshold current densities kA/cm in early May 1977 and quickly wrote a paper describing these results [14]. The first lasers had four cleaved edges and consequently, some of them operated in some total internal reflection mode. Subsequently, I prepared conventional FabryPerot devices using sawed or scribed sides and cleaved facets. I tested some of the diodes using a simple pressure clip mounting and others I used a more normal p-side down bonding scheme using In solder to the p-side and thermo-compression wire bonds to the n-type side. I also submitted a Late News Paper with these first laser results to the 1977 IEEE Solid State Device Research Conference which was held at Cornell University, Ithaca, NY, at the end of June 1977. The Late News Papers were considered on the Sunday before the meeting began. Late Sunday evening, I learned from N. Holonyak that this paper was accepted. R. Dixon (Bell Labs, Murray Hill, NJ) was on the Program Committee and he told me that the paper was accepted with the condition that I tell all about how the results were achieved. I gave my Late Paper in a very full conference room and there were lots of questions about the details of how this work was performed. I could tell there was lots of excitement but there were also lots of skeptics as well. Many of the skeptics were finally convinced later in April 1978 when my paper on the CW operation of MOCVD-grown AlGaAsGaAs lasers was published [15]. These first MOCVD lasers employed a conventional AlGaAsGaAs DH structure. Since the best reliability for LPE lasers reported at that time was being achieved with AlGaAs active regions, after the DRC, I decided to try this type of structure. Furthermore, there were questions regarding the quality of the AlGaAs produced by MOCVD. In early August 1977, I succeeded in operating pulsed AlGaAs DH 0.12 active regions operating lasers with AlGaAs 829 nm, i.e., at significantly shorter wavelengths at nm laser emission of the GaAs active region than the devices I reported earlier [43]. These results were the first to unequivocally establish that MOCVD-grown AlGaAs was of device quality. At the 1977 DRC, my Ph.D. dissertation advisor, Prof. N. Holonyak, Jr., presented another very important laser result. He described the operation at 77 K of LPE-grown injection lasers having a quantum-well active regionthis active region was nm) InGaAsP layers.19 These composed of ultrathin (
19These

Fig. 4. Uniform AlGaAs x 0:80 film grown on 1.5-in diameter sapphire substrate grown in the second reactor. The blue and pink colors are due to the optical interference between the film and the sapphire. Photograph taken February 23, 1977.

results are published in [44].

are the first non-AlGaAs-based quantum-well lasers to operate and the first quantum-well lasers not grown by MBEin fact they were also the first QW diode lasers. After I gave my paper at the DRC, Holonyak suggested the possibility of the growth of ultrathin AlGaAsGaAs heterostructures using my MOCVD reactor. When I described the reactor control and gas switching systems I had built just for the purpose of controlling the growth of abrupt heterointerfaces, he was very surprised that I had such an elaborate system already prepared with the exact capabilities needed to grow such ultrathin layer structures. We immediately began making plans for collaboration on the use of my MOCVD reactor for the growth of AlGaAsGaAs injection lasers using quantum-well heterostructures (QWHs). This led to the study of the interface abruptness of MOCVD-grown AlGaAsGaAs heterojunctions, showing that the interfaces were abrupt to the limits of Auger electron spectroscopy measurements [45], [46]. Other workers had reported difficulties in the MOCVD growth of AlGaAs. For example, Blakeslee and Bischoff [47] reported in 1971 that no PL was observed from AlGaAs ) grown by MOCVD on GaAs substrates while ( Lee et al.reported that the PL spectra for AlGaAs films with showed an intense m deep-level emission [48]. In fact, later in 1978, Stringfellow and Hall had ) alloys grown by reported that AlGaAs ( conventional MOCVD were highly compensated and exhibited no PL emission [49]. In 1978, Hallais et al. reported that the ) heterojuncinterface width of AlGaAsGaAs ( tions was 3065 nm and that such AlGaAs layers were highly resistive if grown at temperatures less than 800 C [50]. These reports clearly showed that growing high-quality abrupt

1046

IEEE JOURNAL ON SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 6, NO. 6, NOVEMBER/DECEMBER 2000

AlGaAsGaAs heterojunctions by MOCVD needed to be done with care. After my laser results were published in late 1977, other workers began to have some success in growing AlGaAs. For example, Nelson et al. reported the successful growth of AlGaAsGaAs solar cells in December 1977 with the cells showing concentrator AM2. 1 (at 933-sun concentration measured outside in Palo Alto, CA) short-circuit currents of 20.9 mA/cm and open-circuit voltages of 1.01 V for AR-coated cells. No data on 1-sun AM2 efficiencies were given, however, and no AM0 data were reported so it is hard to know how these devices compare to my first MOCVD cells[51]. In 1977 and 1978, I grew many AlGaAsGaAs QWH wafers that I sent to Holonyak for photopumping, leading to the first demonstration of photopumped CW quantum-well laser operation at 300 K [52]. Later, we succeeded in injection laser operation of single-QW and multiple-QW structures [53], [54]. This work led to our report of the very first CW 300 K quantum-well lasers, a term that we invented to describe these devices [55]. This opened up many new avenues of work, including the study of graded AlGaAs cladding regions to form graded-index (GRIN) laser structures. Also, we collaborated on a variety of experiments related to the study of phonon coupling to QW laser emission [56]. I was also interested in forming index-guided stripe-geometry lasers using nonplanar growth. Since I was familiar with the kinetically limited nonplanar etching of GaAs using NH OHH O solutions, I used this etch to produce nonplanar substrates to grow AlGaAsGaAs lasers [57]. These channel-guide lasers were grown on etched channels 58 m wide and 250350 nm deep. The AlGaAsGaAs SQW laser structures were grown in these channels, creating a nonplanar QW active region that had higher optical losses for the higher-order transverse-parallel lateral optical modes, resulting in single mode laser operation at 300 K. Later, other workers used this approach of growing on nonplanar V-groove-etched substrates to produce quantum wires, i.e., structures with a one-dimensional confinement of electronhole pairs. Another novel type of laser that I studied is an AlGaAsGaAs injection laser device using distributed Bragg reflectors (DBRs) as cladding layers [58]. This structure employed n- and p-type dielectric stack cladding layers composed of twelve to fourand teen pairs of alternating layers of doped AlGaAs GaAs on each side of an undoped GaAs active region. The absorption edge of the GaAs layers in the mirrors is Bursteinshifted to higher energy due to the high doping concentrations employed in these regions. The DBR period was nm for various wafers. I designed these mirrors using a simple Bragg reflector model and an HP Model 6825A Desktop Computer. These lasers operated in a pulsed mode at 300 K with kA/cm . I believe these were the first epitaxial DBRs ever grown. Later, such epitaxial DBR mirrors would become instrumental in the operation of vertical-cavity surface-emitting lasers (VCSELs). The reliability of MOCVD-grown AlGaAsGaAs lasers was an issue that was frequently brought up at conferences and in discussions that I had with many researchers, including Ralph

Fig. 5.

Large-area MOCVD-grown AlGaAsGaAs QW laser wafer.

Fig. 6. Spectra (300 K) for the first MOCVD-grown AlGaAsGaAs CW injection laser.

Logan, Franz-Karl Reinhart, and others from Bell Labs. Once, in a particularly heated question-and-answer session after one of my talks, B. Hakki (from the Laser Development Group at Bell Labs) asked when I was going to have reliability dataI told him whenever someone would pay me to do the measurements [59]! Later, when I was at Bell Labs, I would work with others (Bob Hartman, Frank Nash, and Lou Koszi) to determine the useful lifetime of AlGaAs QW lasers grown by MOCVD [60]. However, at Rockwell, I had very limited resources to do this type of testingI only had one stable precision current supply to run CW diodes, no diode temperature controllers, no automatic optical output power controllers, and no facet coatings, no diamond heat-sinks or other CW device bonding technology. So one weekend, I set up an MOCVD-grown

DUPUIS: IIIV SEMICONDUCTOR HETEROJUNCTION DEVICES GROWN BY MOCVD

1047

Fig. 7.

Auger-electron spectroscopy profiling analysis of MOCVD-grown AlGaAsGaAs multiple-quantum-well heterostructure showing abrupt interfaces.

AlGaAsGaAs MQW laser diode (the active region had six GaAs QWs and five Al Ga As barriers) to test under constant-current conditions at whatever junction temperature would arise during testing. I went into the testing lab several times during the day and the evenings to check on the diode lifetime. As the result of this testing, I was able to demonstrate over 700 hours of life at room-temperature with virtually no change in output power for such an uncoated laser diode [61]. Even though this diode was not mounted in a sophisticated package, and had over 14 AlGaAsGaAs heterojunctions in the active region, the reliability was shown to be suitable for many applications. In September 1979, at the invitation of Dr. M. B. Panish, I joined the Physics Research Division of AT&T Bell Laboratories in Murray Hill, NJ. I was given some space (five longbays) on the third floor of Building One to build a lab. I designed a lab for materials and device testing and a clean room lab with the gas services, exhaust scrubbers, and wafer cleaning facilities to provide the necessary support to operate two MOCVD systems. After a very long delay created by the construction of the clean room, I designed and built an entirely new MOCVD reactor. Except for the sealing of the base of the quartz growth chamber, this system used all-welded joints, stainless-steel bellows-sealed valves, and all metal-sealed components using either Cajon VCR face-sealed gas fittings or Conflat type metal-sealed vacuum fittings. For the control system, I used dual Tylan 16-channel programmers, which were a more advanced version of the Tylan controller I had used at Rockwell. Furthermore, the entire system was capable of being evacuated with a turbomolecular vacuum pump, which had a large-area liquid N cold trap and quadrupole mass spectrometer attached to it. The reactor system had the capacity for simultaneous operation of eight metalorganic sources and four hydrides, including AsH and PH as well as the dopants H Se and SiH . The RF heated

chamber had a 2.5-in diameter susceptor that could hold one 2.0-in diameter wafer. I again used all-welded 316 stainless steel metalorganic source vessels that I designed and constructed for this purpose. I also installed a Panametrics System I moisture monitor and several probes in the H , AsH , and PH lines to monitor these gases for water vapor content. After this reactor was completed, it did not take long before I had working laser devices. In fact, when I gave my device technician, Phil Foy,20 the first AlGaAsGaAs DH laser wafer I grew with this reactor to process into laser bars, he asked me Will it lase? and I told him Of course! It did! Later, in collaboration with B. Hartman and F. Nash in the Laser Development Department (in Area 20), I worked on MOCVD laser reliability. In May 1983, we submitted a paper describing the first high-reliability MOCVD lasers [62]. These devices were graded-index separate-confinement heterostructure singlequantum-well lasers which exhibited degradation rate less than 1%/kh at 70 C at 5 mW/facet CW output powers. Later, I also grew InP-based materials in this reactor and studied the lattice-matching of InGaAs and InGaAsP materials, as well as the doping and the growth of heterojunctions. I eventually also made InGaAsInP p-i-n photodetectors and InGaAsPInP injection lasers. IV. OTHER DEVELOPMENTS IN MOCVD The limitations of space and the specific subject of this paper have prevented me from describing many of the other important developments leading to the breadth of the current MOCVD technology, among them, the development of low-pressure
20Philip W. Foy was William Shockleys Technician in 1947 and was in Walter Brattians lab when Brattain first saw the gain of the first transistor. He is very skilled and experienced at making semiconductor laser devices, having worked on lasers for many years.

1048

IEEE JOURNAL ON SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 6, NO. 6, NOVEMBER/DECEMBER 2000

MOCVD for the growth of GaAs [63], InP [64], and InGaAsP [65], and the development of the adduct-purification scheme for the purification of metal alkyls [66]. Also, other workers subsequently reported the MOCVD growth of injection lasers, including Veenvleit et al. in October 1978 [67], and Thrush et al. in March 1979 [68] Later, many other groups contributed to the development of the MOCVD injection laser materials and device technologies. Another important development is the use of advanced chemical kinetics, surface kinetics, and hydrodynamics models that can provide for solutions to the multifaceted boundary conditions occurring in a CVD system [69], [70]. The Sandia CVD Sciences Group has provided tools for the detailed analysis of MOCVD systems and they have contributed greatly to the understanding of the large-area commerical MOCVD reactors in common use today. V. FUTURE VISION The MOCVD process has been used for a wide variety of IIIV binary, ternary, quaternary, and pentanary semiconductor films. It has also been used for the growth of oxides, superconductors, dielectrics, and the deposition of metal films, including Cu for electrical interconnects. I expect that the usage in all these areas will increase dramatically in the next few years. One particularly important development is the expansion of the MOCVD growth of IIIN materials, a process also pioneered by Manasevit in 1971 [71]. This application of MOCVD will soon lead to the dramatic expansion of LED-based lighting products into many of the mass-market lighting applications, including the development of high-efficiency white-light solidstate lamps. It is clear that the future development of MOCVD will continue to rely on improvements in the purity of precursors (both organometallics and hydrides). Furthermore, advances in the understanding of chemical reactions, hydrodynamics, precursor kinetics, etc., should lead to improved large-scale reactor designs capable of growing simultaneously on more than a dozen 6-in diameter substrates using a wide range of growth pressures. Furthermore, the efficiencies of scale in the production of metal alkyls should permit the cost factor of precursors to be reduced. MOCVD reactors with kilogram quantities of metal alkyls are now common in production environments. One important aspect of MOCVD (and all other CVD epitaxial growth processes, including CVD for Si) that still remains to be developed is real-time monitoring and process controlwhile some in situ monitoring techniques have been developed, most notably spectroscopic ellipsometry, spectrally resolved reflectivity, and emissivity-corrected pyrometry. These techniques permit some useful degree of real-time monitoring but the missing elementthe real-time control is still sorely needed. One important component to this control loop is the monitoring of the gas-phase and surface species. Techniques for determining gas-phase composition are well established and include laser-induced fluorescence and absorption spectroscopy. The measurement of surface species in a CVD environment is still problematical. Additional complications arise due to the lack of spatial uniformity in the gas phase inside a reactor and

near the growing surface. Real-time three-dimensional chemical mapping of the reactant species inside a CVD growth chamber is a daunting problem and one that will not yield easily using conventional techniques. Many more years of research and development are required to realize a true process control system for MOCVD. However, it is an area of continued activity and research results are being continually translated into commercial products. VI. SUMMARY AND CONCLUSION In the late 1970s, MOCVD was shown to be a viable technology for the growth of high-performance solar cells and sophisticated injection lasers. From this work, it was possible to predict that the MOCVD process would become an important element in the fabrication of a wide variety of high-performance semiconductor devices. Because of the economics and flexibility of the process, the quality of the materials produced, and the scalability of the technology, it has come to dominate the epitaxial growth of IIIV semiconductors. The demonstration of the first room-temperature CW quantum-well injection lasers (grown by MOCVD) was a watershed event that changed the course of IIIV materials technology for optoelectronics and also for electronics. Today, most optical memory systems, (e.g., CD-ROMs, DVD players, etc.) and optical communications systems employ such QW injection lasers based upon MOCVD epitaxial films. In addition, most high-performance digital cellular communications rely on the performance of MOCVD-grown heterojunction bipolar transistors. In the near future, MOCVD will play a dominant role in the lighting market, making MOCVD a household materials technologybut probably not a household word. I remember when explaining the laser device results I had demonstrated using the MOCVD process to one of the Vice Presidents at Rockwell, he told me that he was impressed with the results I had achieved using metal oxide CVD. I told him that it had taken quite some effort to get the oxide out of MOCVD! Somehow MO is always thought of as metal oxide perhaps someday the metalorganic term will be widely known as well. ACKNOWLEDGMENT The author would like to thank Dr. J. Mee for the support and encouragement in the early stages of this work at Rockwell, and Dr. R. P. Ruth who was the Principal Investigator of the ERDA contract. The author also would like to thank Dr. H. M. Manasevit for being very helpful in the beginning phases of his MOCVD research and W. I. Simpson for many useful discussions. It is the authors pleasure to thank many individuals who were directly involved in supporting this research. D. Yingling was involved in the MOCVD growth of low-cost solar cells, and L. A. Moudy provided X-ray characterization of some of the AlGaAsGaAs materials. Dr. J. J. J. Yang helped in the electrical characterization of some of the films grown at Rockwell. F. Kinoshita provided help in metallization of the wafers. Prof. N. Holonyak, Jr., was instrumental in the initiation of and the beginning phases of the work on quantum-well lasers

DUPUIS: IIIV SEMICONDUCTOR HETEROJUNCTION DEVICES GROWN BY MOCVD

1049

and has always been an excellent collaborator and role model to the author for more than thirty years. The training and experience received in Holonyaks lab regarding the approach to solving problems has been useful throughout the authors career. The author also wants to thank some of N. Holonyaks previous graduate students who helped with the early QW laser work, particularly, Dr. R. Chin, Prof. R. M. Kolbas, Dr. W. D. Laidig, Dr. E. A. Rezek, and Dr. B. A. Vojak. Several people at Bell Labs were also instrumental in supporting the work on reliable MOCVD AlGaAsGaAs lasers, in particular, Dr. M. B. Panish, Dr. V. Narayanamurti, and Dr. J. A. Giordmaine. The author also wants to thank his collaborators Dr. R. L. Hartman, Dr. R. C. Miller, Dr. F. R. Nash, Dr. J. van der Ziel, and acknowledge the excellent technical support of P. W. Foy, R. B. Zetterstrom, and J. R. Velebir. Finally, the author wants to thank his wife, D. E. Dupuis, and his daughter, E. A. Dupuis, for their strong support and encouragement over the past years of hard work and during the many nights and weekends that he had been MIA at home (or AWOL) because he was in the laboratory.

REFERENCES
[1] H. M. Manasevit, Single-crystal gallium arsenide on insulating substrates, Appl. Phys. Lett., vol. 12, no. 4, pp. 156159, 1968. [2] T. R. Scott, G. King, J. M. Wilson, and Standard Telecommunications and Cables, Ltd., Improvements in or relating to the production of material for semi-conductors, British patent 778 383, July 3, 1957. [3] W. Miederer, G. Ziegler, R. Dtzer, and Siemens-Schuckertwerke, Method of crucible-free production of gallium arsenide rods from alkyl gallium and arsenic compounds at low temperatures, Patent 3 226 270, Dec. 28, 1965. [4] R. A. Ruehrwein and Monsanto Company, Altering proportions in a vapor deposition process to form a mixed crystal graded energy gap, 3 224 913, Dec. 21, 1965. , Production of epitaxial films of semiconductor compound mate[5] rial, 3 312 570, Apr. 4, 1967. [6] , Production of epitaxial films, 3 312 571, Apr. 4, 1967. [7] H. M. Manasevit and W. I. Simpson, Single-crystal silicon on sapphire substrate, J. Appl. Phys., vol. 35, no. 4, pp. 13491351, 1964. [8] H. M. Manasevit, The use of metalorganics in the preparation of semiconductor materials: Growth on insulating substrates, J. Cryst. Growth, vol. 13/14, pp. 306314, 1972. [9] P. Rai-Choudhury, Epitaxial gallium arsenide from trimethyl gallium and arsine, J. Electrochem. Soc., vol. 116, no. 12, pp. 17451746, 1969. [10] T. Saitoh and S. Minagawa, Epitaxial growth and characterization of pyrolytic grown GaAsP for electroluminescent devices, J. Electrochem. Soc., vol. 120, pp. 656665, 1973. [11] S. Ito, T. Shinohara, and Y. Seki, Properties of epitaxial gallium arsenide from trimethylgallium and arsine, J. Electrochem. Soc., vol. 120, no. 10, pp. 14191423, 1973. [12] R. D. Dupuis, P. D. Dapkus, R. D. Yingling, and L. A. Moudy, High-efficiency GaAlAsGaAs heterostructure solar cells grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 31, no. 3, pp. 201203, 1977. [13] R. D. Dupuis, Room-temperature operation of GaAlAsGaAs doubleheterostructure lasers grown by metalorganic chemical vapor deposition, Late News Paper presented at 35th Annual Device Research Conference, Cornell University, Ithaca, NY, June 1977. [14] R. D. Dupuis and P. D. Dapkus, Room-temperature operation of Ga Al AsGaAs double-heterostructure lasers grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 31, no. 7, pp. 466468, 1977. [15] , Continuous room-temperature operation of Ga Al AsGaAs double-heterostructure lasers grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 32, no. 7, pp. 406407, 1978. [16] , Ga Al AsGa Al As room-temperature lasers grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 31, no. 12, pp. 839841, 1977.

[17] R. Didchenko, J. E. Alix, and R. H. Toeniskoetter, Reactions of phosphine with trimethylindium, J. Inorg. Nucl. Chem., vol. 14, pp. 3537, 1960. [18] B. C. Harrison and E. H. Tompkins, Preparation of indium antimonide and gallium arsenide films, Inorg. Chem., vol. 1, no. 4, pp. 951953, 1962. [19] H. M. Manasevit and W. I. Simpson, The use of metalorganics in the preparation of semiconductor materialsI: Epitaxial gallium-V compounds, J. Electrochem. Soc., vol. 116, no. 12, pp. 17251732, 1969. [20] H. M. Manasevit and Rockwell International Corp., Epitaxial composite and method of making, U.S. Patent 4 368 098, Jan., 11 1983. [21] Rockwell MOCVD patent ruled invalid, Compound Semiconductor, pp. 1415, Mar./Apr. 1997. [22] J. J. Tietjen and J. A. Amick, The preparation and properties of vaporP using arsine and phosphine, J. Elecdeposited epitaxial GaAs trochem. Soc., vol. 113, p. 724, 1966. [23] H. Rupprecht, J. M. Woodall, and G. D. Petit, Efficient visible electroluminescence at 300K from GaAlAs p-n junctions grown by liquid-phase epitaxy, Appl. Phys. Lett., vol. 11, no. 3, pp. 8183, 1967. [24] J. A. Arthur, Vapor pressures and phase equilbria in the Ga-As system, J. Phys. Chem. Solids, vol. 28, p. 2257, 1967. [25] M. Waldner and I. D. Rouse, Gallium arsenide on sapphire field-effect transistors, Proc. IEEE, p. 2066, 1969. [26] H. M. Manasevit, The use of metalorganics in the preparation of semiconductor materialsIII: Studies of IIIV aluminum compound formation using trimethylaluminum, J. Electrochem. Soc., vol. 118, no. 4, pp. 647650, 1971. [27] H. M. Manasevit and W. I. Simpson, The use of metalorganics in the preparation of semiconductor materialsII: IIVI compounds, J. Electrochem. Soc., vol. 118, no. 4, pp. 644647, 1971. , The use of metalorganics in the preparation of semiconductor [28] materialsVI. Formation of IVVI lead and tin salts, J. Electrochem. Soc., vol. 122, no. 3, pp. 444450, 1975. [29] N. Holonyak, Jr., D. C. Jillson, and S. F. Bevacqua, Halogen vapor transport and growth of epitaxial layers of intermetallic compounds and compound mixtures, in Metallurgy of Semiconductor Materials, J. B. Schroeder, Ed. New York: Interscience, 1962, pp. 5059. [30] W. F. Finch and E. W. Mehal, Preparation of GaAs P by vapor phase reaction, J. Electrochem. Soc., vol. 111, no. 11, pp. 814818, 1964. [31] J. J. Tietjen, Vapor-phase growth of several IIIV compound semiconductors, J. Cryst. Growth, vol. 9, no. 1, pp. 149150, 1971. [32] R. Nelson, Epitaxial growth from the liquid state and its application to the fabrication of tunnel and laser diodes, RCA Rev., pp. 603615, Dec. 1963. [33] A. Y. Cho, Morphology of epitaxial growth of GaAs by a molecular beam method: The observation of surface structures, J. Appl. Phys., vol. 41, no. 7, pp. 27802786, 1970. [34] A. Y. Cho and W. C. Bellamy, GaAs planar technology by molecular beam epitaxy, J. Appl. Phys., vol. 46, no. 2, pp. 783785, 1975. [35] R. Tsu, A. Koma, and L. Esaki, Optical properties of semiconductor superlattice, J. Appl. Phys., vol. 46, no. 2, pp. 842845, 1975. [36] Y. Seiki, K. Tanno, K. Iida, and E. Ichiki, Properties of epitaxial GaAs layers from a triethyl gallium and arsine system, J. Electrochem. Soc., vol. 122, no. 8, pp. 11081112, 1975. [37] W. D. Johnston, Jr. and W. M. Callahan, High-performance solar cell material: n-AlAsp-GaAs prepared by vapor phase epitaxy, Appl. Phys. Lett., vol. 28, no. 3, pp. 150152, 1976. [38] Thin films of gallium arsenide on low-cost substrates, ERDA, Contract E(04-3)-1202. [39] J. P. Andre, A. Gallais, and J. Hallais, GaAsGaAlAs heterostructures grown by the metal-alkyl process, in Gallium Arsenide and Related Compounds (Edinburgh)1976. ser. Inst. Phys. Conf. Ser. no. 33a, C. Hilsum, Ed. Bristol: Institute of Physics, 1977, ch. 1, pp. 18. [40] S. J. Bass, Device quality epitaxial gallium arsenide grown by metal alkyl-hydride technique, J. Cryst. Growth, vol. 31, no. 1, pp. 172178, 1975. [41] M. Allenson and S. Bass, GaAs reflection photocathodes grown by metal alkyl vapor phase epitaxy, App. Phys. Lett., vol. 28, no. 3, pp. 113115, 1976. [42] A. M. White, P. J. Dean, and P. Porteous, Photocapacitance effects of deep traps in epitaxial GaAs, J. Appl. Phys., vol. 47, no. 7, pp. 32303239, 1976. [43] R. D. Dupuis and P. D. Dapkus, Ga Al AsGa Al As double-heterostructure room-temperature lasers grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 31, no. 12, pp. 839841, 1977.

1050

IEEE JOURNAL ON SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 6, NO. 6, NOVEMBER/DECEMBER 2000

[44] E. A. Rezek, N. Holonyak, Jr., B. A. Vojak, G. E. Stillman, J. A. Rossi, Ga P As (x 0:12, D. L. Keune, and J. D. Fairing, LPE In z 0:26) DH laser with multiple thin-layer (<500 ) active region, Appl. Phys. Lett., vol. 31, no. 288290, 1977. [45] R. D. Dupuis, L. A. Moudy, and P. D. Dapkus, Preparation and propAl AsGaAs heterojunctions grown by metallorganic erties of Ga chemical vapor deposition, in Gallium Arsenide and Related Compounds1978. ser. Inst. Phys. Conf. no. 45, C. M. Wolfe, Ed. Bristol: Institute of Physics, 1979, ch. 1, pp. 19. [46] R. D. Dupuis, P. D. Dapkus, C. M. Garner, C. Y. Su, and W. E. Spicer, Al AsGaAs quantum-well heterostructures grown by Abrupt Ga metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 34, no. 5, pp. 335337, 1979. [47] A. E. Blakeslee and B. F. Bischoff, Vapor growth of Ga Al As by pyrolysis of alkyls, in Proc. Fall Electrochem. Soc. Mtg., Cleveland, OH, 1971, Abstract 181, pp. 469470. [48] C. H. Lee, H. B. Pogge, and B. M. Kemlage, Preparation and properties of pyrolytic GaAlAs, in Proc. 1971 Fall Electrochem. Soc. Mtg., Cleveland, OH, 1971, Abstract 180, pp. 466468. As, [49] G. B. Stringfellow and H. T. Hall, Jr., VPE growth of Al Ga J. Cryst. Growth, vol. 43, pp. 4760, 1978. [50] J. Hallais, J. P. Andre, P. Baudet, and D. Boccon-Gibod, New MESFET devices based on GaAs(Ga, Al)As heterostructures grown by metallorganic VPE, in Gallium Arsenide and Related Compounds1978. ser. Int. Phys. Conf. no. 45, C. M. Wolfe, Ed. Bristol: Institute of Physics, 19781979, ch. 4, pp. 361370. [51] N. J. Nelson, K. K. Johnson, R. L. Moon, H. A. Vander Plas, and L. W. James, Organometallic-sourced VPE AlGaAsGaAs concentrator solar cells having conversion efficiencies of 19%, Appl. Phys. Lett., vol. 32, no. 1, pp. 2627, 1978. [52] N. Holonyak Jr., R. M. Kolbas, R. D. Dupuis, and P. D. Dapkus, Room-temperature continuous operation of photopumped MO-CVD AsGaAsGaAsAl Ga As quantum-well lasers, Appl. Al Ga Phys. Lett., vol. 33, no. 1, pp. 7375, 1978. [53] R. D. Dupuis, P. D. Dapkus, N. Holonyak, Jr., E. A. Rezek, and R. Chin, Room-temperature laser operation of quantum-well Al AsGaAs laser diodes grown by metalorganic chemical Ga vapor deposition, Appl. Phys. Lett., vol. 32, no. 5, pp. 295297, 1978. [54] N. Holonyak, Jr., R. M. Kolbas, W. D. Laidig, B. A. Vojak, R. D. Dupuis, and P. D. Dapkus, Low-threshold continuous laser opAsGaAs eration (300337K) of multilayer MO-CVD Al Ga quantum-well heterostructures, Appl. Phys. Lett., vol. 33, no. 8, pp. 737739, 1978. [55] R. D. Dupuis, P. D. Dapkus, R. Chin, N. Holonyak, Jr., and S. W. Kirchoefer, Continuous 300 K laser operation of single-quantum-well Al Ga AsGaAs heterostructure diodes grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 34, no. 4, pp. 265267, 1979. [56] B. A. Vojak, N. Holonyak, Jr., R. Chin, E. A. Rezek, R. D. Dupuis, and P. D. Dapkus, Tunnel injection and phononassisted recombination in AsGaAs pn heterostructure lasers multiple quantum-well Al Ga grown by metalorganic chemical vapor deposition, Appl. Phys., vol. 50, no. 9, pp. 58355840, 1979. [57] R. D. Dupuis and P. D. Dapkus, Single-longitudinal-mode cw roomtemperature Ga Al AsGaAs channel-guide lasers grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 33, no. 8, pp. 724726, 1978. [58] , Room-temperature operation of distributed-Bragg-confinement Ga Al AsGaAs lasers grown by metalorganic chemical vapor deposition, Appl. Phys. Lett., vol. 33, no. 1, pp. 6869, 1978. [59] R. D. Dupuis, L. A. Moudy, and P. D. Dapkus, Preparation and properties of Ga Al AsGaAs heterojunctions grown by metalorganic chemical vapor deposition, presented at the Seventh Int. Symp. GaAs Related Mater., St. Louis, MO, Sept. 2427, 1979. [60] R. D. Dupuis, R. L. Hartman, and F. R. Nash, Facet-coated gradedindex separate-confinement-heterostructure single-quantum-well lasers having low degradation rates, (<1% KH) at 70 C, IEEE Electron Device Lett., vol. EDL-4, no. 8, pp. 286288, 1983.

[61] R. D. Dupuis, 700 h continuous room-temperature operation of AsGaAs heterostructure lasers grown by metalorganic Al Ga chemical vapor deposition, Appl. Phys. Lett., vol. 35, no. 4, pp. 311314, 1979. [62] R. D. Dupuis, R. L. Hartman, and F. R. Nash, Facet-coated gradedindex separate confinement-heterostructure single-quantum-well lasers having low degradation rates (<1 Percent/kh) at 70 C, Appl. Phys. Lett., vol. EDL-4, no. 8, pp. 286288, 1983. [63] J. P. Duchemin, M. Bonnet, F. Koelsch, and D. Huyghe, A new method for growing GaAs epilayers by low pressure organometallics, J. Electrochem. Soc., vol. 126, no. 7, pp. 11341142, 1979. [64] J. P. Duchemin, M. Bonnet, G. Beuchet, and F. Koelsch, Organometallic growth of device-quality InP by cracking of In(C H ) and PH at low pressure, in Gallium Arsenide and Related Compounds1978. ser. Inst. Phys. Conf. Ser. no. 45, C. M. Wolfe, Ed. Bristol: Institute of Physics, 1979, ch. 1, pp. 1018. [65] J. P. Duchemin, J. P. Hirtz, M. Razeghi, M. Bonnet, and S. D. Hersee, GaInAs and GaInAsP materials grown by low pressure MOCVD for microwave and optoelectronic applications, J. Cryst. Growth, vol. 55, pp. 6473, 1981. [66] A. C. Jones, Metalorganic precursors for vapor phase epitaxy, J. Cryst. Growth, vol. 129, pp. 728773, 1993. [67] H. Veenvleit, W. J. Bartels, and C. v. Opdorp, VPE growth and analysis of GaAsAlGaAsP double heterostructure laser structures, presented at the 1978 IEEE Int. Semiconductor Laser Conf., San Francisco, CA, Oct. 30Nov. 1, Paper E3. [68] E. J. Thrush, P. R. Selway, and G. D. Henshall, Metalorganic CVD growth of GaAsAlGaAs double heterojunction lasers having low interfacial recombination and low threshold, Electron Lett., vol. 15, pp. 156158, 1979. [69] M. E. Coltrin, R. J. Kee, and J. Miller, A mathematical model of the coupled fluid mechanics and chemical kinetics in a chemical vapor deposition reactor, J. Electrochem. Soc., vol. 131, no. 2, pp. 425434, 1984. [70] R. J. Kee, G. H. Evans, and M. E. Coltrin, Application of supercomputers to modeling fluid transport and chemical kinetics in chemical vapor deposition reactors, in Amer. Chem. Soc. Symp. Series, vol. 353, 1987, p. 334. [71] H. M. Manasevit, F. M. Erdman, and W. I. Simpson, The use of metalorganics in the preparation of semiconductor materialsIV: The nitrides of aluminum and gallium, J. Electrochem. Soc., vol. 118, no. 11, pp. 18641868, 1971.

Russell D. Dupuis (S68SM84F87) received the Ph.D. degree in electrical engineering from the University of Illinois, Urbana-Champaign, in 1973. He currently holds the Judson S. Swearingen Regents Chair in Engineering and is Professor in the Department of Electrical and Computer Engineering and in the Microelectronics Research Center at The University of Texas at Austin. He worked at Texas Instruments, Dallas, TX, from 1973 to 1975. In 1975, he joined Rockwell International, where he was the first to demonstrate that MOCVD could be used for the growth of high-quality semiconductor thin films and devices. He joined AT&T Bell Laboratories in 1979, where he extended his work to the growth of InP-InGaAsP by MOCVD. In 1989, he joined The University of Texas at Austin as a Chaired Professor. His technical specialties include semiconductor materials and devices, epitaxial growth by MOCVD, and heterojunction structures in compound semiconductors. He is currently studying the growth of IIIV compound semiconductor devices by MOCVD, including materials in the InAlGaNGaN, InAlGaAsPGaAs, and InAlGaAsPInP systems. Dr. Dupuis is a member of the NAE and a Fellow of the OSA.