CN1560902A

CN1560902A - Preparation method of ZnO:M2O3 (M=Al,Cr)conducting substrate

Info

Publication number: CN1560902A
Application number: CNA2004100167260A
Authority: CN
Inventors: 寅杭; 杭寅; 宋词; 徐军; 周圣明; 杨卫桥; 王海丽; 严成峰
Original assignee: Shanghai Institute of Optics and Fine Mechanics of CAS
Current assignee: Shanghai Institute of Optics and Fine Mechanics of CAS
Priority date: 2004-03-04
Filing date: 2004-03-04
Publication date: 2005-01-05
Anticipated expiration: 2024-03-04
Also published as: CN1299329C

Abstract

The invention is a manufacturing method for ZnO: M2O3 (M=Al, Cr) conductive substrate. It uses hydroghermal method to synthesize in order to make the compound liquid of ZnO and M2O3 to a fixed saturation, grows ZnO: M2O3 (M=Al, Cr) conductive substrate crystal plate on the ZnO substrate crystal plate seed crystal. The impurity doped ZnO conductive substrate material (ZnO: M2O3) and GaN crystal lattice have a small mismatch performance, the conductivity makes the back of the substrate crystal plate to carry on electrode contact.

Description

ZnO:M 2O 3The preparation method of (M=Al, Cr) conductive substrates

Technical field

The present invention relates to conductive substrate material, particularly a kind of ZnO:M that mainly serves as the growth of InN-GaN blue-light semiconductor material ₂O ₃The preparation method of (M=Al, Cr) conductive substrates.

Background technology

III hi-nitride semiconductor material InN-GaN has excellent characteristic, as the optical transition probability of stable physics and chemical property, high thermal conductance and high electron saturation velocities, direct band gap material a high order of magnitude than indirect band gap, therefore, broad-band gap InN-GaN base semiconductor is demonstrating wide application prospect aspect short-wave long light-emitting diode, laser and ultraviolet detector and the high-temperature electronic device.Because the InN-GaN fusing point is higher, N ₂Saturated vapor pressure is bigger, and InN-GaN body single crystal preparation is very difficult, so InN-GaN generally grows with epitaxy technology on foreign substrate.

White gem crystal (α-Al ₂O ₃) be easy to preparation, low price, and have the good characteristics such as high-temperature stability, α-Al ₂O ₃It is at present the most frequently used InN-GaN epitaxial substrate material (referring to Jpn.J.Appl.Phys., the 36th volume,, the 1568th page in 1997).

Carborundum (SiC) is white stone relatively, with GaN lattice mismatch smaller (2.2%), higher thermal conductivity (3.8w/cm.K) is arranged, and conductivity is arranged, and can simplify the making of device greatly, make semiconductor device miniaturization more, also be that present InN-GaN epitaxial substrate material commonly used is (referring to Solid-State Electron, the 44th volume, 2000, the 1229th page).

Utilize ZnO to obtain extensive studies in recent years as buffer growth GaN film.Because ZnO and GaN lattice mismatch smaller (＜2.0%), and identical stacking order is arranged, ZnO is easy to cleavage in addition, so ZnO is considered to extremely promising InN-GaN backing material.

Backing material formerly has significant disadvantages:

(1) with α-Al ₂O ₃Make substrate, α-Al ₂O ₃And lattice mismatch makes the GaN film of preparation that high bit dislocation density and a large amount of point defects be arranged up to 14% between the GaN;

(2) not soaking into of SiC and GaN makes that the GaN depositing of thin film need be by resilient coating AlN or Al _xGa _1-xN, but these resilient coatings raise the resistivity between device and the substrate;

(3) lattice mismatch of SiC and GaN is still too big, makes that the defect concentration of GaN film is bigger;

(4) SiC hardness height, the substrate surface difficult treatment, and the defective of substrate surface rewinds the defective of GaN epitaxial loayer to increase (referring to Apply.Phys.87,2000 years, the 2725th page); (5) SiC substrate cost height, the SiC monocrystalline also has only a few manufacturers to grow at present.

Summary of the invention

The technical problem to be solved in the present invention is to overcome above-mentioned the deficiencies in the prior art, and a kind of ZnO:M for the growth of InN-GaN blue-light semiconductor material is provided ₂O ₃The preparation method of (M=Al, Cr) conductive substrates, the conductive substrates that the party's legal system is standby and GaN lattice mismatch are little, and its electric conductivity makes the back side of substrate wafer carry out easily electrode contact, thereby has greatly simplified the making of device.And good reproducibility, cost is low.Utilize the ZnO conductive substrate material of the synthetic admixture of hydro-thermal method, i.e. ZnO:M ₂O ₃(M=Al, Cr).

Technical solution of the present invention is as follows:

A kind of ZnO:M ₂O ₃The preparation method of (M=Al, Cr) conductive substrates is characterized in that by synthetic ZnO and the M that makes under the HTHP of hydro-thermal method ₂O ₃(Al ₂O ₃Or Cr ₂O ₃) aqueous solution of mixture reaches certain degree of supersaturation, at the ZnO substrate wafer seed crystal ZnO:M that grows ₂O ₃(M=Al, Cr) conductive substrates wafer.

Described ZnO:M ₂O ₃The preparation method of (M=Al, Cr) conductive substrates comprises the following steps:

1, earlier ZnO powder sintering piece, the Al of some and particle diameter ₂O ₃(or Cr ₂O ₃) the powder sintering piece puts into the dissolve area of autoclave gold sleeve;

2, the mixed solution that adds alkali-metal mineralizer and water by the compactedness of 70%-85%;

3, the trapezoidal seed crystal frame that uses the gold silk to make will couple together with the gold silk by the seed wafer that certain orientation cuts and be fixed on the seed crystal frame;

4, the seed crystal frame is slowly put into gold bushing pipe and good seal, put into autoclave more together, again autoclave is thoroughly sealed and slowly put into resistance furnace, again the sealing of capped steel lid;

5, resistance furnace heats up, and adjusts temperature and pressure, controls required temperature and the temperature difference, reaches the autoclave reaction chamber internal and external equilibrium temperature of design, and is under the constant temperature and grows, and growth cycle is according to amount and admixture ZnO crystal, the i.e. ZnO:M of placement compost ₂O ₃The growth rate of (M=Al, Cr) and deciding;

6, stay-warm case is opened in blowing out, and autoclave is proposed burner hearth, takes out the seed crystal frame, takes out crystal, with warm water the solution on surface is cleaned.

Described dissolve area temperature is 400 ℃, and the vitellarium temperature is 380-390 ℃, 15 ℃ of the temperature difference; Operating pressure 1100atm, in the 10 ℃/h of programming rate, constant temperature growth when the autoclave internal and external temperature reaches balance.

The present invention compares the admixture ZnO conductive substrate material (ZnO:M that grows with technology formerly ₂O ₃) little with the GaN lattice mismatch, its electric conductivity makes the back side of substrate wafer carry out easily electrode contact, thereby has greatly simplified the making of device.And good reproducibility, cost is low, is applicable to batch process.

Description of drawings:

Fig. 1 is that the present invention prepares the used grower generalized section of recombination laser crystalline material.

Embodiment:

The present invention prepares admixture ZnO conductive substrate material with above-mentioned hydrothermal growth method, selected Hydrothermal Growth stove device as shown in Figure 1, and it is made up of the high temperature and high pressure kettle 4 of a tyre stay-warm case and supporting with it temperature difference well formula resistance furnace 10.Its structure mainly comprises: vitellarium 1, dissolve area 2, steel cap 3, steel still 4.In order to prolong the life-span of autoclave 4, prevent the corrosion to the still internal chamber wall under HTHP of acidity or alkaline solution, use gold lining 5 to separate as the protection lining and with autoclave inner-wall.The trapezoidal seed crystal frame 6 that uses the gold silk to make will couple together with the gold silk by the seed wafer that certain orientation cuts and be fixed on the seed crystal frame 6, and whenever next ladder frame can be hung tens of (deciding on the seed crystal size).Gold lining 5 inner chambers have mineralizer 7 and H ₂The mixed solution of O, ZnO and Al ₂O ₃(or Cr ₂O ₃) compost 8 is positioned at dissolve area 2, baffle plate with holes 9 is arranged at compost 8 tops.

Table 1 has been listed specific embodiments of the invention, and the preparation process of these embodiment is as follows:

1, with 1000 gram particles directly is ZnO powder sintering piece, the 100 gram Al of 4-8mm ₂O ₃(or Cr ₂O ₃) the powder sintering piece puts into the dissolve area 2 of gold lining 5 bottoms;

2, press the different schemes preparation mineralizer of table 1 and the mixed solution of water respectively, the compactedness by 70%, 78%, 85% adds the mixed solution of mineralizer 7 and water;

Mineralizer solution and the compactedness of table 1 different schemes

Embodiment	Mineralizer concentration	Compactedness
Embodiment	Mineralizer concentration	Compactedness	1	NaOH (5.5-6.5mol/l)+H ₂O	70%
2	NaOH (5.5-6.5mol/l)+H ₂O	78%	1	NaOH (5.5-6.5mol/l)+H ₂O	70%
2	NaOH (5.5-6.5mol/l)+H ₂O	78%	3	NaOH (5.5-6.5mol/l)+H ₂O	85%
4	KOH (5.5-6.5mol/l)+H ₂O	70%	3	NaOH (5.5-6.5mol/l)+H ₂O	85%
4	KOH (5.5-6.5mol/l)+H ₂O	70%	5	KOH (5.5-6.5mol/l)+H ₂O	78%
6	KOH (5.5-6.5mol/l)+H ₂O	85%	5	KOH (5.5-6.5mol/l)+H ₂O	78%

3, the trapezoidal seed crystal frame made from the gold silk 6, the ZnO seed wafer two ends optical grade polishing of Φ 30 * 30 * 2mm that cuts by (0001) direction spiles at the edge, connects aperture with the gold silk, and is fixed on the seed crystal frame 6.

4, seed crystal frame 6 is slowly put into gold lining 5, and good seal puts into autoclave 4 more together, and slowly put into resistance furnace 10, capped steel lid 3;

5, resistance furnace 10 heats up, and adjusts temperature and pressure.The dissolve area temperature is 400 ℃, and the vitellarium temperature is 380-390 ℃, 15 ℃ of the temperature difference; Operating pressure 1100atm, in the 10 ℃/h of programming rate, the autoclave internal and external temperature reaches balance, and the constant temperature growth is 15 days under this temperature;

6, stay-warm case is opened in cooling, blowing out, and autoclave 4 is proposed burner hearth, takes out crystal block, and crystal is sparkling and crystal-clear transparent, does not have cotton nothing and splits, and integrality is good.

By (0001) section polishing, as the InN-GaN substrate, its electric conductivity makes the back side of substrate wafer carry out the electrode contact easily, thereby has simplified the making of device greatly with the gained crystal, is very desirable in blue light InN-GaN thin film substrate material.

Claims

1, a kind of ZnO:M ₂O ₃The preparation method of (M=Al, Cr) conductive substrates is characterized in that by synthetic ZnO and the M that makes under the HTHP of hydro-thermal method ₂O ₃(Al ₂O ₃Or Cr ₂O ₃) aqueous solution of mixture reaches certain degree of supersaturation, at the ZnO substrate wafer seed crystal ZnO:M that grows ₂O ₃(M=Al, Cr) conductive substrates wafer.

2, ZnO:M according to claim 1 ₂O ₃The preparation method of (M=Al, Cr) conductive substrates is characterized in that comprising the following steps:

＜1〉at first ZnO powder sintering piece, the Al of some and particle diameter ₂O ₃(or Cr ₂O ₃) the powder sintering piece puts into the dissolve area (2) of gold lining (5) bottom;

＜2〉compactedness by 70%-85% adds alkali-metal mineralizer (7) and water mixed solution;

＜3〉the trapezoidal seed crystal frame (6) that uses the gold silk to make, the seed wafer that cuts by certain orientation couples together with the gold silk and is fixed on the seed crystal frame (6);

＜4〉seed crystal frame (6) is slowly put into gold bushing pipe and good seal, put into autoclave more together, again autoclave is thoroughly sealed and slowly put into resistance furnace (10);

＜5〉resistance furnace (10) heats up, and adjusts temperature and pressure, controls required temperature and the temperature difference, reach the autoclave reaction chamber internal and external equilibrium temperature of design, and be under the constant temperature and grow, growth cycle is according to amount and admixture ZnO crystal, the i.e. ZnO:M of placement compost (8) ₂O ₃The growth rate of (M=Al, Cr) and deciding;

＜6〉stay-warm case is opened in blowing out, and autoclave is proposed burner hearth, takes out seed crystal frame () and takes out crystal, with warm water the solution on surface is cleaned.

3, ZnO:M according to claim 2 ₂O ₃The preparation method of (M=Al, Cr) conductive substrates, its feature

Be that described dissolve area temperature is 400 ℃, the vitellarium temperature is 380-390 ℃, 15 ℃ of the temperature difference; Operating pressure 1100atm, in the 10 ℃/h of programming rate, constant temperature growth when the autoclave internal and external temperature reaches balance.