Austin Lane 1/31/12

The Fabrication of GaAs by the Bridgman Growth Technique

The horizontal Bridgman (HB) growth technique is a bulk semiconductor fabrication technique, typically used to grow compound semiconductors such as gallium arsenide (GaAs). The Bridgman growth technique was invented in the 1920s by Percy Williams Bridgman, a Harvard physicist whose primary work dealt with observing matter under high pressures.[1] Folberth and Weiss were the first to use a horizontal furnace to grow GaAs in 1955.[2] Their apparatus, which consisted of a boat inside of a quartz tube and moved through a two-zone temperature furnace, resembles the Bridgman apparatus seen today. A typical horizontal Bridgman growth apparatus consists of a boat made of quartz or boron nitride; this boat holds the polycrystalline GaAs precursor and also supports the GaAs crystal during growth. This boat is surrounded by a quartz ampoule, which is kept under vacuum for the duration of the process. A furnace surrounds the ampoule and is responsible for maintaining constant temperatures within the various temperature zones of the apparatus. The Bridgman process is typically divided into two temperature zones; one which contains the GaAs precursor and another which contains a small amount of solid As. Because As is more volatile than Ga, evaporation of As from the surface of the crystal will produce a non-stoichiometric concentration of Ga:As within the melt, unless measures are taken to counteract this effect. The purpose of the solid As is to ensure that the stoichiometric ratio of Ga:As is maintained at the crystal growth site. A desirable vapor pressure for As is 1 atm, which requires a temperature of ~ 618 C. At the start of the reaction, the GaAs precursor is heated to a temperature of 1238 C or greater, which is enough to melt the GaAs but not the quartz boat.[3] The solid As precursor is kept at its sublimation temperature of ~618C to ensure the a constant As overpressure of 1 atm throughout the reaction. These two zones are typically separated by a glass wool plug within the ampoule. This plug serves as a convection barrier to help maintain the desired As overpressure.[4] In more modern Bridgman growth processes, a third temperature zone will exist in between the other two temperature zones and is kept at a temperature of 1100-1200 C. The primary purpose of this zone is decrease the size of the temperature gradient between the GaAs region and the solid As region. Before the reaction takes place, a seed crystal is placed at one end of the boat. This crystal serves as an initial growth site, which defines the crystallographic orientation of the larger single crystal (typically (111)). The GaAs formation reaction takes place at the surface of the GaAs melt and the seed crystal, where both Ga and As diffuse through the boundary layer to react together. To initiate crystal growth, the furnace is slowly moved away from the seed crystal at a speed of 15-20 mm/hr along the axial direction of the ampoule.[5] GaAs crystallizes as the seed cools and enters an annealing zone within the furnace. This annealing zone is maintained at a temperature of 1100-1200C, then the crystal enters a cooling zone where temperatures equal 800C or less. The cooling rate of the GaAs in this zone is 10-30C/hour, with a final cooling rate of 80C/hr down to room temperature. Throughout the process, the temperature gradient at the front of the growing crystal is kept between 2-5 C/cm.

Compared to the Czochralski growth method, the Bridgman growth method can produce crystals with fewer dislocations (102 cm-2) due to the smaller thermal gradients present in the melt. However, the main disadvantage of the Bridgman technique is the interaction between the boat and the crystal. The quartz boat can cause impurities and defects on the outside of the crystal.[5] Due to the elevated temperatures, SiO2 can react with Ga to produce GaOx, an unwanted impurity for device manufacture. It can also produce defects due to a mismatch of crystal structures at the interface between the crystal and the quartz boat. To alleviate the defects, the quartz boat is sand-blasted or rinsed in HF before running a new reaction.[3] The boat can even be placed in a Ga bath at 1100 C under a Ar to coat the inner surface of the boat with a protective layer of Ga. The boat also forces the final crystal to have a D-shaped cross-section, which is disadvantageous for device production. GaAs wafers made from the horizontal Bridgman growth technique cannot be produced larger than 75 mm for this reason. The vertical Bridgman growth technique has since been developed to eliminate these interactions between the boat and the crystal. Instead of a boat, the GaAs precursor and solid As are in direct contact with the ampoule, which is held vertically inside of the reactor furnace. This allows the crystal to be grown in a cylindrical shape, allowing for more efficient device fabrication. However, growing the GaAs directly inside the ampoule also presents a new problem, as GaAs will expand when cooled. As it expands to fill the ampoule, thermal stresses tend to produce dislocations and even fracturing within the crystal. Despite this drawback, the vertical growth technique is highly favored in industry today, mainly because of the ability to produce circular wafers more efficiently.[3] Another variation of the Bridgman growth technique is the horizontal gradient freeze technique. Also known as Chalmers method, this process uses a fixed furnace and a moving ampoule instead of a moving temperature zone. The primary disadvantage of this method is the moving ampoule produces small mechanical vibrations during crystal growth which leads to dislocations once the crystal has cooled.[3] This is the primary reason that the Bridgman growth technique is favored over any gradient freeze method. In conclusion, the Bridgman growth technique has many advantages for growing compound semiconductors such as GaAs. Most notably, the Bridgman process produces single crystals with low thermal stresses, which directly relates to the dislocation density in the final product. Crystals grown using this method typically have dislocation densities of 102 cm-2, much lower than crystals produced using the liquid-encapsulated Czochralski technique (6000 cm-2). However, the Bridgman growth technique cannot produce circular wafers more that 2-3 inches in diameter. It also requires maintaining precise control of the stoichiometry at the growth site, as a stoichiometric reaction is critical for single crystal growth. A stoichiometric ratio of Ga to As can be achieved by charging the ampoule with solid As and maintaining a temperature of ~ 618 C to produce an overpressure of As at the crystal growth site. A clean and defect-free boat is also necessary for single crystal growth, since the melt is direct contact with the boat during growth. Although antiquated by the vertical Bridgman growth technique in industry today, the horizontal Bridgman growth technique has remained an important process in the development of GaAs semiconductors.

References
1. Kemble, Edwin, and Francis Birch. Percy Williams Bridgman, A Biographical Memoir. 1st ed. Washington D.C.: National Academy of Sciences, 1970. eBook. 2. Folberth, Og, and H. Weis. "Herstellung Und Elektrische Eigenschaften Von Inp Und GaAs." Zeitschrift fr Naturforschung. A, Astrophysik, Physik und physikalische Chemie 10.8 (1955):615-619. 3. Chen, Tzer-Perng. Modified Horizontal Bridgman Method for Growing GaAs Single Crystal. 4,902,376. (20 Feb., 1990).
4. Campbell, Stephen. Fabrication Engineeering at the Micro- and Nano-scale . 3rd ed.

New York City: Oxford University Press, 2008. eBook.

5. Ghandhi, Sorab. VLSI Fabrication Principles. 2nd ed. New York: John Wiley & Sons,

Inc., 1994. Print.