WO2016101388A1

WO2016101388A1 - Preparation method of compound semiconductor thin-film material

Info

Publication number: WO2016101388A1
Application number: PCT/CN2015/072140
Authority: WO
Inventors: 刘兴泉; 刘一町; 张铭菊; 张峥; 赵红远; 何永成; 张怀武
Original assignee: 电子科技大学
Priority date: 2014-12-26
Filing date: 2015-02-03
Publication date: 2016-06-30
Also published as: CN104498896A

Abstract

The present invention relates to a preparation method of a compound semiconductor thin-film material. A large-scale preparation of the compound semiconductor target thin-film material can be realized via a one-step method of the present invention, preparing a plurality of thin films at once, having a short preparation period, a high preparation efficiency and a low preparation cost, being well adapted to a substrate (base sheet) material without requiring special processing of the substrate (base sheet) thereof; the compound semiconductor thin-film material prepared via a two-step method has a high purity and good crystallinity; a sealing system is employed in the preparation process, thus avoiding raw material loss caused by sublimation, and having high process controllability; and the preparation temperature is lower, thus reducing energy consumption.

Description

Method for preparing compound semiconductor film material

Technical field

The present invention relates to the field of film material manufacturing, and in particular to a method for preparing a compound semiconductor film material having a composition of Ga _δ In _1-δ P _y As _1-y [0 _≤ _δ _≤ _{1, 0 ≤ y ≤ 1} ].

Background technique

Gallium arsenide (GaAs) is a synthetic compound semiconductor material with a band gap of 1.42 eV at room temperature. GaAs is a sphalerite crystal lattice structure with a lattice constant of 5.65×10 ^-10 m and a direct transition energy band structure with indium phosphide (InP). Gallium arsenide is a dark gray solid with a melting point of 1238 °C. It is below 600 ° C and is stable in air and is not attacked by non-oxidizing acids.

Gallium arsenide is a material that has many advantages in semiconductor materials. Gallium arsenide entered a substantive application stage in 1964. Gallium arsenide can be made into a semi-insulating high-resistance material with a resistivity higher than three orders of magnitude higher than that of silicon and germanium. It is used to fabricate integrated circuit substrates, infrared detectors, and gamma photon detectors. Since its electron mobility is 5-6 times larger than that of silicon, it has become an important application in the fabrication of microwave devices and high-speed digital circuits. The semiconductor device made of gallium arsenide has the advantages of high frequency, high temperature, low temperature performance, low noise, strong radiation resistance and the like. In addition, it can also be used to make transfer device-body effect devices.

GaAs has some better electronic properties than Si, allowing GaAs to be used above 250 GHz. If the equivalent GaAs and Si components operate at high frequencies at the same time, GaAs produces less noise. At the same time, because GaAs has a high breakdown voltage, GaAs is more suitable for operation in high power than the same Si component. Due to these characteristics, GaAs circuits can be used in mobile phones, satellite communications, microwave point-to-point connections, radar systems, and the like. GaAs was used to make Gann diodes, microwave diodes, and Gunn diodes to emit microwaves. Since GaAs is a direct band gap semiconductor material, it can be used for light emission. While Si is an indirect bandgap material, it can only emit very weak light. Therefore, GaAs has a wide application prospect in LEDs.

Gallium arsenide plays an important role in the contemporary microelectronics and optoelectronics industries. 50% of its products are used in military and aerospace applications, 30% for communications, and the rest for network equipment, computers and test instruments. Due to its excellent high frequency characteristics, GaAs is widely used in the manufacture of wireless communication and optical communication devices. Insulating gallium arsenide single crystals have become the main materials for manufacturing high-power microwave, millimeter-wave communication devices and integrated circuits. For optical radiation, solar cells, infrared detectors, mobile communications, fiber optic communications, cable television, satellite communications, automotive radar, infrared LEDs, high-brightness red, orange, yellow LEDs, semiconductor laser diodes, military night vision and aerospace High efficiency solar cells.

According to the prediction of Silicon Valley Strategy, the global demand for wireless communication devices based on GaAs materials in 2000 is 1.7 billion US dollars, of which the demand for gallium arsenide polishing wafers and epitaxial wafers is 600 million US dollars, and will reach 25 in 2005. Billion dollars, the annual growth rate reached 30%.

Since gallium arsenide can process photoelectric data simultaneously on the same chip, it is widely used in many fields of optoelectronics such as remote control, mobile phones, DVD computer peripherals, and illumination. In addition, because its electron mobility is six times higher than that of silicon, gallium arsenide is a necessity for ultra-high-speed, ultra-high-frequency devices and integrated circuits. It is also widely used in the military field and is an important material for laser guided missiles.

Another important application of GaAs is the high efficiency of solar cells. In 1970, Zhores Alferov and his team made the first GaAs heterostructure solar cell in the Soviet Union. A three-interface solar cell made of GaAs, Ge, and InGaP has an efficiency of more than 32% and can operate at 2,000 suns. This type of solar cell has been used on robots that detect the surface of Mars: the spirit rover and the opportunity rover. And many solar cells are battery arrays made of GaAs.

Gallium phosphide (GaP) is also a synthetic III-V compound semiconductor material, and high purity GaP is an orange-red transparent crystal. The gallium phosphide (GaP) single crystal material has a melting point of 1467 °C. The crystal of gallium phosphide (GaP) is still a zinc blende structure with a lattice constant of 0.5447±0.006nm. The chemical bond is a mixed bond mainly composed of covalent bonds. The ionic bond component is about 20%. The gap (Eg) is 2.26 eV, which is an indirect transition type semiconductor. Gallium phosphide (GaP) is the same as other large band gap III-V compound semiconductors, and the Fermi level can be approached to the middle of the band gap by introducing a deep center. For example, a rare insulating material such as chromium, iron or oxygen can be used as a semi-insulating material. . Gallium phosphide (GaP) is classified into a single crystal material and an epitaxial material. Industrially produced substrate single crystals are N-type semiconductors doped with sulfur and silicon impurities.

The GaP single crystal was prepared by a liquid phase method at normal pressure in the early stage. It is then prepared by liquid-covered straight pull method. The gallium phosphide (GaP) single crystals produced by the modern semiconductor industry are all synthesized in a high-pressure synthesis furnace by a directional solidification process, and are appropriately processed and then loaded into a high-pressure single crystal furnace for single crystal drawing. The gallium phosphide epitaxial material is obtained by liquid phase epitaxy or vapor phase epitaxy and diffusion growth on a gallium phosphide single crystal substrate. GaP is mostly used to manufacture light emitting diodes (LEDs). Liquid phase epitaxial material can produce red light, yellow green light, pure green A light-emitting diode, a vapor phase epitaxy and a diffusion-grown material, can produce a yellow, yellow-green light-emitting diode.

Indium phosphide (InP) is still a semiconductor material formed by combining Group IIIA elements In and VA group elements P. The forbidden band width of indium phosphide at room temperature is 1.35 eV, which is the same as the direct transition type band structure of GaP. Indium phosphide (InP) is a dark gray crystal with asphalt luster, melting point 1070 ° C, still belongs to the zinc blende structure.

The dissociation pressure of indium phosphide (InP) at the melting point was 2.75 MPa. Very slightly soluble in inorganic acids. The dielectric constant is 10.8. The electron mobility was 4600 cm ² /(V·s). The hole mobility was 150 cm ² /(V·s). Has the characteristics of a semiconductor. It was first produced by heating a metal indium and red phosphorus in a quartz tube. Indium phosphide is used as a semiconductor material and can be used in optical fiber communication technology.

The history of commercial production of semiconductor technology can be seen as a history of continuous improvement and renewal of a series of process technologies. The first commercial transistor was made of germanium (Ge), but in the early 1960s, silicon (Si) devices quickly surpassed it in performance and price. The reason why silicon semiconductors can now establish a dominant position in the semiconductor industry is due in part to the continuous development of process technology, which makes silicon devices highly competitive in terms of integrated functionality and price. The third commercial semiconductor technology emerged in the late 1980s from the field of compound materials - gallium arsenide (GaAs), but due to the complexity and difficulty of gallium arsenide preparation, people are still looking for a substitute for arsenic. Gallium compound semiconductor technology for high performance, high volume commercial applications. Now a new compound semiconductor device has begun to appear, this is indium phosphide (InP) and its derivatives, which form the fourth wave of semiconductor material development. Indium phosphide semiconductors have clearly demonstrated convincing performance advantages over gallium arsenide in fiber fabrication, millimeter wave, and even wireless applications. We believe these advantages will open the gap between indium phosphide and other materials, and ultimately replace silicon and gallium arsenide as the best choice for compound semiconductor technology.

The above conventional compound semiconductor thin film materials are conventionally prepared by using molecular beam epitaxy (MBE) or metal-organic vapor phase epitaxy (MOVPE), also known as metal organic chemical vapor deposition. (metal-organic chemical vapor deposition, MOCVD). Single crystals of compound semiconductors (such as GaAs) can also be fabricated using Horizontal Bridgeman (HB) technology and Czochralski method.

In addition, the preparation method of the III-V compound type semiconductor thin film material also includes an expensive and demanding physical method and a complicated and expensive MOCVD method, and the former is obtained by reacting a high-purity IIIA main group metal with a high-purity VA main group non-metal. A corresponding compound semiconductor film such as the reaction formula (1). Physical methods such as plasma sputtering, molecular beam epitaxy (MBE), electron beam evaporation (EBE), pulsed laser deposition (PLD), magnetron sputtering (MSD), and the like. The latter is prepared by reacting an expensive IIIA main group metal organic compound (liquid or gaseous) such as trimethylgallium (or indium) with a highly toxic compound of the VA main group (such as gaseous arsane AsH ₃ , phosphine PH ₃ ). A compound semiconductor film such as the reaction formula (2). Their principles and chemical reactions are as follows:

M(III)+N(V)→M(III)N(V) (1)

M(III)(CH ₃ ) ₃ +N(V)H ₃ →M(III)N(V)+3CH ₄ (2)

Summary of the invention

One technical problem to be solved by the present invention is to provide a compound semiconductor target film material which can be prepared on a large scale, and a plurality of films are prepared at one time, and the preparation cycle is short, and the substrate (substrate) material is highly adaptable, and the substrate is not required. (Substrate) A method of preparing a semiconductor film material that is specially treated.

To achieve the above object, a method for preparing a compound semiconductor thin film material of the present invention is any one of the following two steps: A, B, C or D:

A: Step 1: Mix the Ga ₂ O ₃ and As oxides with a molar ratio of Ga:As=1:1, grind uniformly, add 50%-100% absolute ethanol with the mass of the solid raw material, and grind evenly at room temperature. Vacuum drying to obtain a solid powder, which is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, sealed in a vacuum quartz ampoule, and then placed in a reactor corundum crucible and heated in a tube furnace. After 500 ° C ~ 600 ° C, constant temperature 2 ~ 4h, natural cooling to obtain the reaction product;

Step 2. Break the vacuum quartz ampoule, place the reaction product in the reaction zone of the thin film deposition apparatus, place the substrate in the deposition zone of the thin film deposition apparatus, replace it with high purity nitrogen gas to the oxygen concentration of ppm, and then use Ar. The H ₂ mixed gas is vacuum-displaced 2 to 3 times, and then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, the reaction zone is heated to 1000 ° C to 1250 ° C, and the deposition zone is heated to 600 ° C. ~800 °C, open the substrate rotating device, set the speed of 5 rev / min, pass hydrogen, as a reducing extractant, constant temperature for 2 ~ 4h, during which the vacuum degree ≥ -0.08MPa; finally cool down to room temperature, fill Ar , H ₂ mixed gas to atmospheric pressure, the surface of the substrate is deposited with a GaAs film material;

B: mixing Ga ₂ O ₃ and P ₂ O ₅ by molar ratio of Ga: P=1:1, grinding uniformly, adding anhydrous ethanol with 50% to 100% of the mass of the solid raw material, grinding again and drying, using 10 Pressing the pressure to -15 MPa, then sealing it into a vacuum ampule, placing the ampoules in the reactor corundum, heating in a tubular electric furnace to 500 ° C ~ 600 ° C, constant temperature 2 ~ 4 h, Naturally cooled to GaPO ₄ ;

Step 2. Break the vacuum quartz ampule, place the GaPO ₄ in the reaction zone of the thin film deposition apparatus, place the substrate in the deposition zone of the thin film deposition apparatus, and replace it with a high purity nitrogen gas to a concentration of ppm, then use Ar. +H ₂ mixed gas is vacuumed and replaced 1 or 2 times, then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, the reaction zone is heated to 1200 ° C to 1250 ° C, and the deposition zone is heated to 600 ° C. °C ~ 800 °C, open the substrate rotating device, set the speed of 5 rev / min, pass hydrogen, as a reducing extractant, constant temperature for 3 ~ 4h, during which the vacuum degree ≥ -0.08Mpa; then naturally cool to room temperature, charge a high-purity Ar+H ₂ mixed gas to atmospheric pressure, and a GaP film material is deposited on the surface of the substrate;

C: Step 1. In ₂ O ₃ , P ₂ O ₅ is used as a raw material, and the molar ratio is mixed in the ratio of In:P=1:1 to 2, and anhydrous ethanol equivalent to 50% to 100% of the mass of the solid raw material is added. After grinding uniformly, the solvent is removed by drying, pressed into a sheet with a pressure of 10 to 15 MPa, and then sealed in a vacuum ampule, heated in a tubular electric furnace to 500 ° C to 600 ° C, at a constant temperature of 2 to 4 h, and naturally cooled. Obtaining InPO ₄ solid material;

Step 2. Break the vacuum ampule and place the InPO ₄ solid material in the reaction zone of the thin film deposition apparatus. The substrate is preset in the deposition zone of the thin film deposition apparatus, and is replaced with high purity nitrogen gas to the oxygen concentration of ppm. The mixed gas of Ar and H ₂ is vacuum-displaced 1 to 2 times, and then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, and the reaction zone is heated to 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C ~ 800 ° C, open the substrate rotating device, set the speed of 5 rev / min, pass high purity hydrogen, as an extractive reducing agent, constant temperature 3 ~ 4h, during which the vacuum degree ≥ -0.08Mpa, and finally naturally cool to room temperature , that is, the InP film material is obtained;

D: Step 1: Mix the In ₂ O ₃ and As oxides with a molar ratio of In: As = 1:1, grind uniformly, add 50% to 100% of absolute ethanol with the mass of the solid raw material, and grind evenly at room temperature. Vacuum drying to obtain a solid powder, which is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, sealed in a vacuum quartz ampoule, and then placed in a reactor corundum crucible and heated in a tube furnace. After 500 ° C ~ 600 ° C, constant temperature 2 ~ 4h, natural cooling to obtain the reaction product;

Step 2. Break the vacuum quartz ampoule, place the reaction product in the reaction zone of the thin film deposition apparatus, place the substrate in the deposition zone of the thin film deposition apparatus, replace it with high purity nitrogen gas to the oxygen concentration of ppm, and then use Ar. The H ₂ mixed gas is vacuum-displaced 2 to 3 times, and then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, the reaction zone is heated to 1000 ° C to 1250 ° C, and the deposition zone is heated to 600 ° C. ~800 °C, open the substrate rotating device, set the speed of 5 rev / min, pass hydrogen, as a reducing extractant, constant temperature for 2 ~ 4h, during which the vacuum degree ≥ -0.08MPa; finally cool down to room temperature, fill Ar , H ₂ mixed gas to atmospheric pressure, the surface of the substrate is deposited with InAs film material.

Preferably, the oxide of As is As ₂ O ₃ or As ₂ O ₅ , and the corresponding reaction product is GaAsO ₃ or GaAsO ₄ .

Preferably, the sheet has a thickness of 1 to 10 mm.

Preferably, the Ar, H ₂ H ₂ gas mixture by volume of 10% to 30% of the total volume of the mixed gas.

Preferably, the reducing extractant in step 2 uses a hydrogen-argon mixture, activated carbon or hydrocarbon.

Preferably, when activated carbon is used as the reducing extractant, the solid activated carbon should be placed in the reaction zone of the thin film deposition apparatus.

The principle and chemical reaction of the two-step method of the present invention are as shown in the reaction formulas (3), (4), (5), (6), (7), (8):

M(III) ₂ O ₃ +N(III) ₂ O ₃ →2M(III)N(III)O ₃ (3)

M(III) ₂ O ₃ +N(V) ₂ O ₅ →2M(III)N(V)O ₄ (4)

2 M(III)N(III)O ₃ +6H ₂ →2 M(III)N(V)+6H ₂ O↑ (5)

2 M(III)N(V)O ₄ +8H ₂ →2 M(III)N(V)+8H ₂ O↑ (6)

2 M(III)N(V)O ₄ +4C→2M(III)N(V)+4CO↑ (7)

2 M(III)N(V)O ₄ +2C→2 M(III)N(V)+2CO ₂ ↑ (8)

By changing the type and proportion of the extraction extractant, both CO emissions and CO ₂ emissions can be produced in the product.

The two-step method of the invention has simple raw materials, is cheap and easy to obtain, is solid or non-toxic gas, has no pollution to the environment, has no safety threat to the operator; the preparation equipment is simple, the preparation period is short, and the substrate (substrate) The material has strong adaptability and low preparation cost, and can realize preparation of a large-scale compound semiconductor film material.

The compound semiconductor film prepared by the invention has high purity and good crystallinity; a sealing system is adopted in the preparation process to avoid loss of raw materials due to sublimation, and M(III)N(V)O ₄ or 2M(III) can be formed according to stoichiometric ratio. N(III)O ₃ ; high controllability of the process; and lower preparation temperature, saving energy.

Another technical problem to be solved by the present invention is to provide a compound semiconductor film material with high purity and good crystallinity; a sealing system is adopted in the preparation process to avoid loss of raw materials due to sublimation, and the process controllability is high; and the preparation temperature is lower. A method of preparing a semiconductor film material that saves energy.

In order to achieve the above object, a method for preparing a compound semiconductor thin film material of the present invention is characterized in that it adopts any one of the next steps E, F, G or H:

E: Ga ₂ O ₃ , As ₂ O ₃ and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled in a ratio of Ga..As..C=1.0..1.2..6.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature for 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, after filling the Ar + H ₂ mixed gas to normal pressure, the gray-black GaAs film is obtained;

F: In ₂ O ₃ , P ₂ O ₅ and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled in the ratio of In..P..C=1.0..1.0..4.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature for 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, after filling the Ar + H ₂ mixed gas to normal pressure, the gray-black InP film is obtained;

G: Ga ₂ O ₃ , P ₂ O ₅ and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled at a ratio of Ga..P..C=1.0..1.0..8.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature for 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, after filling the Ar + H ₂ mixed gas to normal pressure, the orange-red GaP film is obtained;

H: In ₂ O ₃ , As ₂ O ₃ and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled in the ratio of In..As..C=1.0..1.2..6.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, filled with Ar + H ₂ mixed gas to normal pressure, the gray-black InAs film is obtained.

Preferably, the volume of H _{2 in} the mixed gas accounts for 10% to 30% of the total volume of the mixed gas.

The principle and chemical reaction of the one-step method of the present invention are as shown in the reaction formulas (9) and (10):

Ga ₂ O ₃ +As ₂ O ₃ +6C→2GaAs+6CO (9)

Ga ₂ O ₃ +As ₂ O ₃ +6H ₂ →2GaAs+6H ₂ O (10)

In the above reaction, CO and H ₂ O may be produced and discharged.

By adopting the one-step technical scheme of the invention, the compound semiconductor target film material can be prepared on a large scale, and multiple films are prepared at one time, and the preparation period is short, and the substrate (substrate) material has strong adaptability, and the substrate is not required. Tablet) Special treatment.

The main process parameters of the preparation method of the present invention and the conventional or existing compound semiconductor thin film material preparation method are shown in Table 1 below. Take GaAs as an example.

Table 1 Comparison of main process parameters of GaAs conventional or existing methods and methods

The invention has the advantages that the raw materials used are simple, cheap and easy to obtain, and all are solid or non-toxic gases, have no pollution to the environment, have no safety threat to the operator, can be prepared on a large scale, and the film size and thickness can be controlled. High efficiency and low cost.

DRAWINGS

1 is an XRD diffraction spectrum of a GaP film material prepared in Example 1 (two-step method);

2 is an XRD diffraction spectrum of a GaP film material prepared in Example 2 (one-step method);

3 is an XRD diffraction spectrum of the InP film material prepared in Example 3 (two-step method);

4 is an XRD diffraction spectrum of the InP film material prepared in Example 4 (one-step method);

5 is an XRD diffraction spectrum of a GaAs thin film material prepared in Example 5 (two-step method);

6 is an XRD diffraction spectrum of a GaAs thin film material prepared in Example 6 (one-step method);

7 is an XRD diffraction spectrum of the InAs thin film material prepared in Example 7 (two-step method);

Figure 8 is an XRD diffraction spectrum of the InAs film material prepared in Example 8 (one-step method).

detailed description

The above and other technical features and advantages of the present invention are described in more detail below in conjunction with the embodiments.

Example 1

Method and process for preparing GaP by two-step method

A method of preparing a GaP film material, comprising the steps of:

Step 1. Accurately weigh Ga ₂ O ₃ and P ₂ O ₅ with one-tenth of an electronic analytical balance. Mix the molar ratio of Ga/P=1.0/1.0 and grind it evenly. Add 50% of the mass of the solid raw material. Absolute ethanol, after careful grinding again, dry and remove the solvent, press it into a 3 mm thick disc or square piece with a pressure of 12 MPa, then seal it in a vacuum ampule, and place the ampoules in the reactor corundum In the crucible, heated to 500 ° C in a tubular electric furnace, constant temperature 2 h, natural cooling to obtain GaPO ₄ solid material, confirmed by XRD diffraction analysis results;

Step 2. Break the ampoule, place the GaPO ₄ in the reaction zone in the vertical gradient condensing film deposition device, place the substrate in the specified position in the deposition zone of the thin film deposition device, and replace it with high purity nitrogen to the oxygen concentration below ppm. Then, using Ar + H ₂ mixed gas (containing H ₂ volume percentage of 10% to 30%), vacuum replacement is performed twice, then vacuuming to about 1 mmHg, controlling the heating rate to 5 ° C / min, and heating the reaction zone to At 1250 ° C, the deposition zone is heated to 800 ° C; when the temperature of the reaction zone reaches the predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm; hydrogen gas is introduced as a reducing extractant, and the temperature is maintained for 4 hours, and the vacuum is maintained therebetween. Not less than -0.08Mpa; finally, naturally cool down to room temperature, fill the high-purity Ar+H ₂ mixed gas to normal pressure, open the exhaust valve, then open the deposition device, remove the deposited substrate, and obtain the orange-red GaP/substrate film material. .

The prepared GaP film material was analyzed by Japanese R&D XRD, and its XRD diffraction spectrum is shown in Fig. 1. The analysis results show that the GaP film material is a pure phase GaP single phase with high crystallinity and high purity. The film thickness was measured by a step meter, and the result was equivalent to the calculated value, and the thickness was about 2 to 20 μm.

Example 2

Method and process for preparing GaP by one-step method

Accurately weigh Ga ₂ O ₃ , P ₂ O ₅ , activated carbon C with a ratio of one-tenth of an electronic analytical balance, and mix and grind in a ratio of Ga..P..C=1.0..1.0..8.0, and add 50 masses of solid raw materials. % equivalent of absolute ethanol, after careful grinding, press it into a disc of thickness 1mm with a pressure of 10MPa, then place it in the reactor corundum, and replace it with high purity nitrogen to the oxygen concentration of ppm. Above the level, and then substituting the Ar+H ₂ mixed gas (containing 10% of H _{2 by} volume) for 1 time, the substrate required for deposition is processed and placed in a predetermined position in the reactor, and then evacuated to 1 mmHg. Left and right, the heating rate is controlled at 5 ° C / min, heating is started to increase to 1200 ° C in the reaction zone, the deposition zone is 600 ° C, the substrate rotation device is turned on, the rotation speed is set to 5 rpm, the temperature is 3 h, and the vacuum is maintained at not less than -0.08. MPa. Then, it is naturally cooled to room temperature, filled with a high-purity Ar+H ₂ mixed gas to a normal pressure, and then the exhaust gas valve is opened, and then the reactor is opened, and the deposited substrate is taken out to obtain an orange-red GaP film.

The film was analyzed by Japanese R&D XRD. The film was a pure phase of high crystallinity and high purity pure phase GaP phase. The XRD diffraction spectrum is shown in Fig. 2.

Example 3

Method and process for preparing InP by two-step method

A method of preparing a GaP film material, comprising the steps of:

Step 1. Accurately weigh In ₂ O ₃ and P ₂ O ₅ with one-tenth of an electronic analytical balance. Mix the molar ratio of In:P=1.0:1.0-1.5 and grind evenly. Add 50% of the solid material quality. ~100% equivalent of absolute ethanol, after careful grinding again, dry and remove the solvent, press it into a thickness of 3mm with a pressure of 10 ~ 15MPa, then seal it in a vacuum ampule, place the ampoules In the reactor corundum crucible, in a self-made tubular electric furnace, heated to 500 ° C ~ 600 ° C, constant temperature 2 ~ 4h, natural cooling, that is, InPO ₄ solid material;

Step 2. Break the ampoule, place the InPO ₄ solid material in the reaction zone of the vertical gradient condensing film deposition device, and replace it with high purity nitrogen gas to the oxygen concentration of ppm or higher, and then use the Ar+H ₂ mixed gas (including H ₂ volume percentage is 10% to 30%) Vacuum replacement 1 or 2 times, the 6 layers of substrate required for deposition are processed and placed in a predetermined position in the deposition area of the deposition apparatus; then vacuumed to about 1 mmHg to start heating The temperature is raised to 1200 ° C ~ 1250 ° C in the reaction zone, the heating rate is controlled at 5 ~ 10 ° C / min, the deposition zone is 600 ° C ~ 800 ° C, the heating rate is controlled at 5 ~ 10 ° C / min; when the reaction zone, the deposition zone temperature reaches the predetermined temperature After that, the substrate rotating device is turned on, the rotation speed is 5 rpm, and high-purity hydrogen is introduced as a reducing extractant at a constant temperature of 3 to 4 hours, during which the vacuum degree is maintained at ≥ -0.08 Mpa; finally, the temperature is naturally cooled to room temperature, and charged with high purity Ar. After the +H ₂ mixed gas is brought to normal pressure, the exhaust gas valve is opened, the device is opened, and the deposited substrate is taken out to obtain an InP/substrate film.

The prepared InP film was analyzed by Japanese R&D XRD, and the film was a high crystallinity and high purity InP single phase; the XRD diffraction spectrum thereof is shown in Fig. 3.

Example 4

Method and process for preparing InP by one-step method

Accurately weigh In ₂ O ₃ , P ₂ O ₅ , activated carbon C with one-tenth of an electronic analytical balance, and mix and grind in a ratio of In..P..C=1.0..1.0..4.0, and add 50 masses of solid raw materials. % equivalent of absolute ethanol, after careful grinding, press it into a 3mm thick disc with a pressure of 10MPa, dry it, and then place it in the reactor corundum or quartz crucible, and replace it with high purity nitrogen. The oxygen concentration is above the ppm level, and then the vacuum is replaced once with the Ar+H ₂ mixed gas (containing 10% to 30% by volume of H ₂ ), and the substrate required for deposition is processed and placed in the reactor in advance. position. Then vacuuming to about 5Pa, the heating rate is controlled at 5 °C / min, heating is started to increase to 1200 ° C in the reaction zone, the deposition zone is 600 ° C ~ 800 ° C, the substrate rotating device is turned on, the set speed is 5 rpm, the temperature is 3 h, The degree of vacuum maintained therebetween is not less than -0.08 MPa. Then, the temperature is naturally lowered to room temperature, and the high-purity Ar+H ₂ mixed gas is charged to a normal pressure, the exhaust valve is opened, the reactor is opened, and the deposited substrate is taken out to obtain a dark gray InP film;

The film was analyzed by Japanese R&D XRD, and the film was a pure phase InP single phase with high crystallinity and high purity. The XRD diffraction spectrum is shown in Figure 4.

Example 5

Method and process for preparing GaAs by two-step method

A method of preparing a GaAs thin film material, comprising the steps of:

Step 1. Accurately weigh Ga ₂ O ₃ and As ₂ O ₃ with one-tenth of an electronic analytical balance. Mix the molar ratio of Ga/As=1.0/1.0 and grind it evenly. Add 50% of the mass of the solid raw material. Anhydrous ethanol, carefully ground, uniformly dried under vacuum at room temperature to obtain a white solid powder, which is pressed into a 3 mm thick disc or square piece with a pressure of 12 MPa, and then sealed in a vacuum quartz ampoule, and then placed in an ampoule. In the reactor corundum crucible, heated to 600 ° C in a tube furnace, constant temperature 2h, natural cooling to obtain the reaction product GaAsO ₃ ;

Step 2. Break the ampule, and place the reaction product GaAsO ₃ obtained in step 1 in the reaction zone of the vertical gradient condensing film deposition device. After the appropriate deposition, the substrate is pre-placed in the specified position in the deposition device; Nitrogen was vacuum-displaced to an oxygen concentration of ppm, and then replaced with Ar+H ₂ mixed gas (containing 10% to 30% by volume of H ₂ ), and then vacuumed to about 1 mmHg (7 to 13 Pa). The heating rate is controlled at 5 ° C / min, the heating is started to increase to 1250 ° C in the reaction zone, the substrate rotating device is turned on, the set rotation speed is 5 rpm, the heating rate is controlled at 5 ° C / min, and the heating temperature in the deposition zone is heated to about 600 ° C. After reaching the set temperature, turn on the substrate rotating device, set the rotation speed 5 rev / min, pass hydrogen, constant temperature 2 ~ 4h, during which the vacuum is not less than -0.08MPa; finally cool down to room temperature, fill high purity After the Ar+H ₂ mixed gas is brought to normal pressure, the exhaust gas valve is opened, and the deposited substrate is taken out to obtain a gray-black GaAs/substrate film material.

The prepared GaAs film material was analyzed by Japanese R&D XRD, and its XRD diffraction spectrum is shown in Fig. 5. The analysis results show that the GaAs film material has a pure phase GaAs single phase with high crystallinity and purity. The film is measured by a step thickness gauge and has a thickness equivalent to about 0.5 to 10 μm.

Example 6

The method and process for preparing GaAs in one step are as follows.

Accurately weigh Ga ₂ O ₃ , As ₂ O ₃ , activated carbon C with one-tenth of an electronic analytical balance, and mix and grind evenly at a ratio of Ga/As/C=1.0/1.2/6.0. As As is easy to sublimate, As The ratio is slightly excessive, and anhydrous ethanol equivalent to 50% of the mass of the solid raw material is added. After careful grinding, it is pressed into a disc having a thickness of 3 mm with a pressure of 10 MPa, and then placed in a reactor corundum. High-purity nitrogen is vacuum-displaced to an oxygen concentration of ppm, and then replaced with an Ar+H ₂ mixed gas (containing 10% by volume of H ₂ ), and the substrate required for deposition is pretreated in the reaction. Specify the position in the device, then evacuate to 7Pa, the heating rate is controlled at 5 °C / min, start heating to 1200 ° C in the reaction zone, the deposition zone is 600 ° C, constant temperature 3 ~ 4h, during which the vacuum is not less than -0.08MPa; After the reaction zone temperature reaches the predetermined temperature, the substrate rotating device is turned on until the end of the reaction, and then naturally cooled to room temperature, and the high-purity Ar+H ₂ mixed gas is charged to the normal pressure, the exhaust gas valve is opened, the reactor is opened, and the deposited substrate is taken out. That gets grayish black GaAs film.

The film was analyzed by Japanese R&D X/D XRD diffractometer. The film was a pure phase GaAs single phase with high crystallinity and high purity. The XRD diffraction spectrum is shown in Fig. 6.

Example 7

Method and process for preparing InAs by two-step method

A method of preparing an InAs film material, comprising the steps of:

Step 1. Accurately weigh In ₂ O ₃ and As ₂ O ₃ with one-tenth of an electronic analytical balance. Mix the molar ratio of In/As=1.0/1.0 and grind it evenly. Add 50% of the mass of the solid raw material. Anhydrous ethanol, carefully ground, uniformly dried under vacuum at room temperature to obtain a white solid powder, which is pressed into a 3 mm thick disc or square piece with a pressure of 12 MPa, and then sealed in a vacuum quartz ampoule, and then placed in an ampoule. In the reactor corundum crucible, heated to 600 ° C in a tube furnace, constant temperature 2h, natural cooling to obtain the reaction product InAsO ₃ ;

Step 2. Break the ampule, and place the reaction product InAsO ₃ obtained in step 1 in the reaction zone of the vertical gradient condensing film deposition device. After the appropriate deposition, the substrate is pre-placed in the specified position in the deposition device; Nitrogen was vacuum-displaced to an oxygen concentration of ppm, and then replaced with Ar+H ₂ mixed gas (containing 10% to 30% by volume of H ₂ ), and then vacuumed to about 1 mmHg (7 to 13 Pa). The heating rate is controlled at 5 ° C / min, the heating is started to increase to 1250 ° C in the reaction zone, the substrate rotating device is turned on, the set rotation speed is 5 rpm, the heating rate is controlled at 5 ° C / min, and the heating temperature in the deposition zone is heated to about 600 ° C. After reaching the set temperature, turn on the substrate rotating device, set the rotation speed 5 rev / min, pass hydrogen, constant temperature 2 ~ 4h, during which the vacuum is not less than -0.08MPa; finally cool down to room temperature, fill high purity After the Ar+H ₂ mixed gas is brought to normal pressure, the exhaust gas valve is opened, and the deposited substrate is taken out to obtain a gray InAs/substrate film material.

The prepared InAs thin film material was analyzed by Japanese Science D/max XRD, and its XRD diffraction spectrum is shown in Fig. 7. The analysis results show that the GaAs thin film material has a pure phase InAs single phase with high crystallinity and high purity. The film is measured by a step thickness gauge and has a thickness equivalent to about 2 to 10 μm.

Example 8

The method and process for preparing InAs in one step are as follows.

Accurately weigh In ₂ O ₃ , As ₂ O ₃ , activated carbon C with one-tenth of an electronic analytical balance, and mix and grind in a ratio of In/As/C=1.0/1.2/6.0. As As is easy to sublimate, As The ratio is slightly excessive, and anhydrous ethanol equivalent to 50% of the mass of the solid raw material is added. After careful grinding, it is pressed into a disc having a thickness of 3 mm with a pressure of 10 MPa, and then placed in a reactor corundum. High-purity nitrogen is vacuum-displaced to an oxygen concentration of ppm, and then replaced with an Ar+H ₂ mixed gas (containing 10% by volume of H ₂ ), and the substrate required for deposition is pretreated in the reaction. Specify the position in the device, then evacuate to 7Pa, the heating rate is controlled at 5 °C / min, start heating to 1200 ° C in the reaction zone, the deposition zone is 600 ° C, constant temperature 3 ~ 4h, during which the vacuum is not less than -0.08MPa; After the reaction zone temperature reaches the predetermined temperature, the substrate rotating device is turned on until the end of the reaction, and then naturally cooled to room temperature, and the high-purity Ar+H ₂ mixed gas is charged to the normal pressure, the exhaust gas valve is opened, the reactor is opened, and the deposited substrate is taken out. , that is, get the gray InA s film.

The film was tested and analyzed by the Japanese Science D/max XRD diffractometer. The film was a pure phase InAs single phase with high crystallinity and high purity. The film was measured by a step thickness gauge and the calculated value was about 0.5-2.0 μm. between. XRD diffraction spectrum is shown in Figure 8.

The embodiments described above are only intended to describe the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various embodiments of the present invention may be made by those skilled in the art without departing from the spirit of the invention. Modifications and improvements are intended to fall within the scope of the invention as defined by the appended claims.

Claims

A method for preparing a compound semiconductor thin film material, characterized in that it is any one of the following two steps: A, B, C or D:

A: Step 1: Mix the Ga 2 O 3 and As oxides with a molar ratio of Ga:As=1:1, grind uniformly, add 50%-100% absolute ethanol with the mass of the solid raw material, and grind evenly at room temperature. Vacuum drying to obtain a solid powder, which is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, sealed in a vacuum quartz ampoule, and then placed in a reactor corundum crucible and heated in a tube furnace. After 500 ° C ~ 600 ° C, constant temperature 2 ~ 4h, natural cooling to obtain the reaction product;

Step 2. Break the vacuum quartz ampoule, place the reaction product in the reaction zone of the thin film deposition apparatus, place the substrate in the deposition zone of the thin film deposition apparatus, replace it with high purity nitrogen gas to the oxygen concentration of ppm, and then use Ar. The H 2 mixed gas is vacuum-displaced 2 to 3 times, and then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, the reaction zone is heated to 1000 ° C to 1250 ° C, and the deposition zone is heated to 600 ° C. ~800 °C, open the substrate rotating device, set the speed of 5 rev / min, pass hydrogen, as a reducing extractant, constant temperature for 2 ~ 4h, during which the vacuum degree ≥ -0.08MPa; finally cool down to room temperature, fill Ar , H 2 mixed gas to atmospheric pressure, the surface of the substrate is deposited with a GaAs film material;

B: mixing Ga 2 O 3 and P 2 O 5 by molar ratio of Ga: P=1:1, grinding uniformly, adding anhydrous ethanol with 50% to 100% of the mass of the solid raw material, grinding again and drying, using 10 Pressing the pressure to -15 MPa, then sealing it into a vacuum ampule, placing the ampoules in the reactor corundum, heating in a tubular electric furnace to 500 ° C ~ 600 ° C, constant temperature 2 ~ 4 h, Naturally cooled to GaPO 4 ;

Step 2. Break the vacuum quartz ampule, place the GaPO 4 in the reaction zone of the thin film deposition apparatus, place the substrate in the deposition zone of the thin film deposition apparatus, and replace it with a high purity nitrogen gas to a concentration of ppm, then use Ar. +H 2 mixed gas is vacuumed and replaced 1 or 2 times, then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, the reaction zone is heated to 1200 ° C to 1250 ° C, and the deposition zone is heated to 600 ° C. °C ~ 800 °C, open the substrate rotating device, set the speed of 5 rev / min, pass hydrogen, as a reducing extractant, constant temperature for 3 ~ 4h, during which the vacuum degree ≥ -0.08MPa; then naturally cool to room temperature, charge a high-purity Ar+H 2 mixed gas to atmospheric pressure, and a GaP film material is deposited on the surface of the substrate;

C: Step 1. In 2 O 3 , P 2 O 5 is used as a raw material, and the molar ratio is mixed in the ratio of In:P=1:1 to 2, and anhydrous ethanol equivalent to 50% to 100% of the mass of the solid raw material is added. After grinding uniformly, the solvent is removed by drying, pressed into a sheet with a pressure of 10 to 15 MPa, and then sealed in a vacuum ampule, heated to 500 ° C to 600 ° C in a tubular electric furnace, and kept at a constant temperature for 2 to 4 hours, and naturally cooled. Obtaining InPO 4 solid material;

Step 2. Break the vacuum ampule and place the InPO 4 solid material in the reaction zone of the thin film deposition apparatus. The substrate is preset in the deposition zone of the thin film deposition apparatus, and is replaced with high purity nitrogen gas to the oxygen concentration of ppm. The mixed gas of Ar and H 2 is vacuum-displaced 1 to 2 times, and then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, and the reaction zone is heated to 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C ~ 800 ° C, open the substrate rotating device, set the speed of 5 rev / min, pass high purity hydrogen, as an extractive reducing agent, constant temperature 3 ~ 4h, during which the vacuum degree ≥ -0.08MPa, and finally naturally cool to room temperature , that is, the InP film material is obtained;

D: Step 1: Mix the In 2 O 3 and As oxides with a molar ratio of In: As = 1:1, grind uniformly, add 50% to 100% of absolute ethanol with the mass of the solid raw material, and grind evenly at room temperature. Vacuum drying to obtain a solid powder, which is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, sealed in a vacuum quartz ampoule, and then placed in a reactor corundum crucible and heated in a tube furnace. After 500 ° C ~ 600 ° C, constant temperature 2 ~ 4h, natural cooling to obtain the reaction product;

Step 2. Break the vacuum quartz ampoule, place the reaction product in the reaction zone of the thin film deposition apparatus, place the substrate in the deposition zone of the thin film deposition apparatus, replace it with high purity nitrogen gas to the oxygen concentration of ppm, and then use Ar. The H 2 mixed gas is vacuum-displaced 2 to 3 times, and then vacuumed to 7 to 13 Pa, the temperature rising rate is controlled to 5 to 10 ° C / min, the reaction zone is heated to 1000 ° C to 1250 ° C, and the deposition zone is heated to 600 ° C. ~800 °C, open the substrate rotating device, set the speed of 5 rev / min, pass hydrogen, as a reducing extractant, constant temperature for 2 ~ 4h, during which the vacuum degree ≥ -0.08MPa; finally cool down to room temperature, fill Ar , H 2 mixed gas to atmospheric pressure, the surface of the substrate is deposited with InAs film material.
The method for preparing a compound semiconductor thin film material according to claim 1, wherein the oxide of As is As 2 O 3 or As 2 O 5 , and the corresponding reaction product is GaAsO 3 or GaAsO 4 .
The method of producing a compound semiconductor thin film material according to claim 1, wherein the sheet has a thickness of from 1 to 10 mm.
The method of preparing a compound semiconductor thin film material according to claim 1, wherein: said Ar, H 2 H 2 gas mixture by volume of 10% to 30% of the total volume of the mixed gas.
The method for preparing a compound semiconductor thin film material according to claim 1, wherein in the step 2, the reducing extractant is a hydrogen-argon mixed gas, activated carbon or a hydrocarbon.
The method for preparing a compound semiconductor thin film material according to claim 5, wherein when activated carbon is used as the reducing extractant, the solid activated carbon is placed in the reaction zone of the thin film deposition apparatus.
A method for preparing a compound semiconductor thin film material, characterized in that it adopts any one of the next steps E, F, G or H:

E: Ga 2 O 3 , As 2 O 3 and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled in a ratio of Ga..As..C=1.0..1.2..6.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature for 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, after filling the Ar + H 2 mixed gas to normal pressure, the gray-black GaAs film is obtained;

F: In 2 O 3 , P 2 O 5 and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled in the ratio of In..P..C=1.0..1.0..4.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature for 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, after filling the Ar + H 2 mixed gas to normal pressure, the gray-black InP film is obtained;

G: Ga 2 O 3 , P 2 O 5 and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled at a ratio of Ga..P..C=1.0..1.0..8.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature for 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, after filling the Ar + H 2 mixed gas to normal pressure, the orange-red GaP film is obtained;

H: In 2 O 3 , As 2 O 3 and activated carbon C are used as raw materials, and the molar ratio is uniformly mixed and milled in the ratio of In..As..C=1.0..1.2..6.0, and is added in an amount equivalent to 50% to 100% of the mass of the solid raw material. Anhydrous ethanol, after being uniformly ground, is pressed into a sheet having a thickness of 1 to 10 mm under a pressure of 10 to 15 MPa, and then placed in a corundum crucible of the reactor, and the substrate is pretreated and placed in a thin film deposition apparatus. In the deposition zone, evacuate with high-purity nitrogen, replace it with oxygen concentration of ppm, then replace it with vacuum by mixed gas for 1~2 times, evacuate to 7~13Pa, and control the heating rate in the range of 5-10 °C/min. The reaction zone is heated to a temperature of 1200 ° C to 1250 ° C, and the deposition zone is heated to a temperature of 600 ° C to 800 ° C. When the temperature of the reaction zone reaches a predetermined temperature, the substrate rotating device is turned on, and the rotation speed is set to 5 rpm. Constant temperature 3 ~ 4h, during which the vacuum is not less than -0.08MPa; naturally cool to room temperature, filled with Ar + H 2 mixed gas to normal pressure, the gray-black InAs film is obtained.
The method for preparing a compound semiconductor thin film material according to claim 7, wherein the volume of H 2 in the mixed gas accounts for 10% to 30% of the total volume of the mixed gas.