CN1527412A - Composite substrate material of conductive spinel structure MgIn2O4/MgO and its prepn - Google Patents
Composite substrate material of conductive spinel structure MgIn2O4/MgO and its prepn Download PDFInfo
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- CN1527412A CN1527412A CNA031510817A CN03151081A CN1527412A CN 1527412 A CN1527412 A CN 1527412A CN A031510817 A CNA031510817 A CN A031510817A CN 03151081 A CN03151081 A CN 03151081A CN 1527412 A CN1527412 A CN 1527412A
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Abstract
The composite substrate material of conductive spinel structure MgIn2O4/MgO is constituted via setting one layer of covering MgIn2O4 layer onto the monocrystalline MgO. The preparation process of the composite substrate material includes the first RF magnetically controlled sputtering to prepare In2O3 film on monocrystalline MgO substrate, and the subsequent solid reaction between In2O3 and MgO at high temperature to form covering MgIn2O4 layer on the monocrystalline MgO substrate. The composite substrate material of the present invention has simple preparation process, and MgIn2O4 has small lattice mismatching degree to GaN (111) and is transparent conducting oxide material. The composite MgIn2O4/MgO substrate is suitable for epitaxial growth of high quality GaN.
Description
Technical field
The present invention relates to the epitaxially grown conduction spinel structure of a kind of InN-GaN of being applicable to base blue-light semiconductor MgIn
2O
4/ MgO compound lining material and preparation method thereof.
Background technology
The broad-band gap III-V group iii v compound semiconductor material that with GaN is representative is receiving increasing concern, they will be at blue, green light LED (LEDs) and laser diode (LDs), high density information read-write, subsurface communication, deep quest, laser printing, biology and engineering in medicine, and ultrahigh speed microelectronic component and hyperfrequency microwave device aspect are with a wide range of applications.
Because GaN fusing point height, hardness is big, saturated vapor pressure is high, so want the GaN body monocrystalline of growing large-size to need high temperature and high pressure, Polish high pressure research center has made just under the high pressure of 1600 ℃ high temperature and 20kbar that bar is wide to be the GaN body monocrystalline of 5mm.Current, the technology of GaN body monocrystalline of growing large-size more immature, and growth is with high costs, from practical application quite long distance is arranged still.
Sapphire 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).
The MgO crystal belongs to cubic system, and NaCl type structure, lattice constant are 0.4126nm, and fusing point is 2800 ℃.Because the lattice mismatch of MgO crystal and GaN reaches 13%, and not enough stable in MOCVD atmosphere, thereby use less.
At present, typical GaN base blue-ray LED is made on Sapphire Substrate.Its structure is as follows from top to bottom: p-GaN/AlGaN barrier layer/InGaN-GaN quantumwells/AlGaN barrier layer/n-GaN/4 μ m GaN.Because sapphire has high resistivity, so the n-type of device and p-type electrode must be drawn from the same side.This has not only increased the manufacture difficulty of device, has also increased the volume of device simultaneously.According to interrelated data, for the Sapphire Substrate of a slice 2 inches diameter size, present technology can only be produced about about 10,000 of GaN device, and if backing material has suitable conductivity, then when simplifying device making technics, its number can increase to present 3～4 times.
In sum, technology substrate (α-Al formerly
2O
3And MgO) the remarkable shortcoming that exists is:
(1) with α-Al
2O
3Make substrate, α-Al
2O
3And the lattice mismatch between the GaN makes the GaN film of preparation have higher dislocation density and a large amount of point defects up to 14%;
(2) because the lattice mismatch of MgO crystal and GaN reaches 13%, and stable inadequately in MOCVD atmosphere, thereby use less;
(3) above transparent oxide substrate is all non-conductive, and the element manufacturing difficulty is big, has also increased the volume of device simultaneously, has caused the waste of great deal of raw materials.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the shortcoming of above-mentioned prior art, provides a kind of as the epitaxially grown conduction spinel structure of InN-GaN base blue-light semiconductor MgIn
2O
4/ MgO compound lining material and preparation method thereof.
Conduction spinel structure MgIn of the present invention
2O
4/ MgO compound lining material is actually at the MgO monocrystalline and is provided with one deck MgIn
2O
4And consist of, this compound substrate is suitable for epitaxial growth high quality InV-GaN base blue-light semiconductor film.
Report translucent conduction CdO film first in 1907, caused people's big interest; But up to World War II, because military demand, transparent conductive oxide (transparent conductive oxide, TCO) just paid attention to widely and used by film.In decades subsequently, found and studied the TCO film of a variety of materials, and constantly expanded their purposes.
At present, the TCO film is mainly used in flat-panel monitor and building two big fields.In
2O
3: Sn (tin-doped indium oxide, ITO) film has that the transparency is good, resistivity is low, easy erosion is drawn and the easy advantage such as low temperature preparation, is the preferred material of the TCO film that uses in the field of flat panel displays always.SnO
2: the F film is because Heat stability is good, characteristics such as chemical stability is good, hardness is high, production equipment is simple, process cycle is short, the prices of raw and semifnished materials are cheap and production cost is low, in large tracts of land TCO films for building such as Energy Saving Windows are used, has the absolute predominance that can not be substituted.
But, in the different application of TCO film neck city, different requirements has been proposed for the performance of TCO film.And each TCO material all has characteristic separately, can not satisfy all application requirements.For example, transparency electrode in the flat-panel monitor requires the TCO film to have characteristics such as lower resistivity, easily etching, surfacing is smooth, so ito thin film meets its requirement most; But, ito thin film expensive and not corrosion resistance make it on glass of building market at all can't with SnO
2: the F film contends with.
In order to develop the TCO film that is fit to special purpose, some research groups make up various TCO materials, prepare the TCO film that some have new feature.Because the polynary TCO film that the TCO combination of materials consists of can be adjusted electricity, optics, chemistry and the physical property of film by changing component, thereby obtain the not available performance of single TCO material, satisfies the needs of some special occasions.
MgIn
2O
4(Indium magnesium oxide, IMO) is ternary TCO material, MgIn
2O
4Belong to inverse spinel structure, natural magnesium aluminate (MgAl
2O
4) crystal structure of a kind of uniqueness of having is called as spinel structure, this structure belongs to cubic system, face-centered cubic lattice.The chemical species of spinel structure is various, can roughly reduce three types by the calking distribution situation of metal ion in crystal structure: positive spinel type structure, inverse spinel structure, osculant spinel structure.Because this structural difference, the crystal of most of positive spinel type structures is insulators, and the crystal conduction performance of most of inverse spinel structures is good, and some of them can be used as semiconductor substrate materials, for example MgIn
2O
4The conductive capability of the crystal of osculant spinel structure is not as good as the crystal of inverse spinel structure.The MgIn of inverse spinel structure
2O
4Belong to cubic system, lattice paprmeter is 0.8864nm, the about 3.5eV of its optical band gap (being optical energy gap), and room-temperature conductivity can reach 2.3 * 10
2S/cm.
MgIn
2O
4Littler with the lattice mismatch of GaN (111), be 1.1%.But consider MgIn
2O
4Large scale bulk growth difficulty, the present invention proposes to utilize rf magnetron sputtering (radio frequencymagnetron-sputtering notes the sputtering into RF magnetron by abridging) technology and In
2O
3And the method for solid phase reaction takes place between the MgO, generate MgIn in the MgO single crystalline substrate
2O
4Cover layer, thus MgIn obtained
2O
4/ MgO compound substrate.Here, the MgO monocrystalline was both participated in solid phase reaction as reactant, worked again the MgIn that supports on it
2O
4The effect of electrically conducting transparent thin layer.Compound substrate (the MgIn of this kind structure
2O
4/ MgO) be suitable for the epitaxial growth of high-quality GaN.
Basic thought of the present invention is:
A kind of conduction spinel structure MgIn
2O
4The preparation method of/MgO compound lining material mainly is to utilize radio frequency magnetron sputtering method to prepare In in the MgO single crystalline substrate
2O
3Film then at high temperature, passes through In
2O
3With the solid phase reaction of MgO, form MgIn in the MgO single crystalline substrate
2O
4Cover layer.
MgIn of the present invention
2O
4The preparation method of/MgO compound lining material, it comprises following concrete steps:
＜1〉on the MgO single crystalline substrate, prepares In
2O
3Film: the MgO single crystalline substrate of will polish, cleaning is sent into magnetic control sputtering device, and the base vacuum pressure of instrument system is 2 * 10
-3Pa, the radio-frequency power scope is 100-250W, target is by the In of purity 〉=99.99%
2O
3Powder forms through the briquetting sintering, and target diameter is 85mm, thickness 3mm, and target is set to 300mm to the distance of substrate, the sputter high-purity argon gas of purity 〉=99.999%, ar pressure is 6.6 * 10
-2Pa, substrate are the MgO single-chip of twin polishing, and underlayer temperature is a room temperature, and thin film deposition speed is that (close 38 /min), adopt quartz crystal oscillator sheet monitoring deposition rate, film thickness is 500nm to 0.063nm/s.
＜2〉In
2O
3Solid phase reaction with MgO: the In that the upper step was obtained
2O
3/ MgO sample is put into annealing furnace, is warming up to 700～1500 ℃, in the reaction atmosphere of rich In, makes In
2O
3With MgO solid phase reaction taking place at high temperature, obtains MgIn
2O
4Cover layer forms MgIn
2O
4/ MgO compound lining material.
Described In
2O
3The purity of target is better than 99.99%.
Described In
2O
3When with MgO solid phase reaction taking place, the optimum temperature in the annealing furnace is 1000 ℃.
Characteristics of the present invention are:
(1) proposed a kind of for the epitaxially grown MgIn of InN-GaN base blue-light semiconductor
2O
4Backing material, this substrate is compared with substrate formerly, the lattice mismatch littler (being 1.1%) of itself and GaN (111), and this MgIn
2O
4Be transparent conductive oxide (TCO) material.
(2) the present invention proposes to utilize radiofrequency magnetron sputtering technology and In
2O
3And the solid phase reaction between the MgO generates MgIn in the MgO single crystalline substrate
2O
4Cover layer, thus MgIn obtained
2O
4/ MgO compound substrate, the preparation technology of this compound substrate is simple, easy to operate, the compound substrate (MgIn of this kind structure
2O
4/ MgO) be suitable for the epitaxial growth of high-quality GaN.
Description of drawings
Fig. 1 is the schematic diagram of magnetic control sputtering device.
Embodiment
Fig. 1 is the schematic diagram of magnetic control sputtering device.The mechanism of sputter is Ar
+Behind electric field acceleration, become high energy incoming particle bump In
2O
3Target, the part momentum is passed to target atom, this target atom collides with other target atoms again, form cascade process, the target atom of some near surface obtains outwards enough momentum of motion in this cascade process, leave target and sputtered out, drop on the MgO single crystalline substrate of placing from the surperficial number centimeters of target, thereby adhere to, the accumulation deposit becomes In
2O
3Film.Common sputtering method, sputtering yield are not high, add the ionization efficient that magnetic field can increase argon gas (Ar), thereby improve sputtering yield.
Radiofrequency magnetron sputtering technology of the present invention prepares compound lining material MgIn
2O
4The concrete technology flow process of/MgO is as follows:
＜1〉on the MgO single crystalline substrate, prepares In
2O
3Film: the MgO single crystalline substrate of will polish, cleaning is sent into magnetic control sputtering device, and the base vacuum pressure of instrument system is 2 * 10
-3Pa, the radio-frequency power scope is 100-250W, target is by the In of purity 〉=99.99%
2O
3Powder forms through the briquetting sintering, and target diameter is 85mm, thickness 3mm, and target is set to 300mm to the distance of substrate, the sputter high-purity argon gas of purity 〉=99.999%, ar pressure is 6.6 * 10
-2Pa, substrate are the MgO single-chip of twin polishing, and underlayer temperature is a room temperature, and thin film deposition speed is that (close 38 /min), adopt quartz crystal oscillator sheet monitoring deposition rate, film thickness is 500nm to 0.063nm/s.
＜2〉then with In obtained in the previous step
2O
3/ MgO sample is put into annealing furnace, is warming up to 700～1500 ℃, in order to suppress In
2O
3Volatilization, adopt the reaction atmosphere of rich In, In
2O
3With MgO solid phase reaction taking place at high temperature, has obtained MgIn
2O
4Cover layer, the selective annealing temperature also by the control annealing time, through evidence, all can obtain having the MgIn of different-thickness in 700～1500 ℃
2O
4Cover layer obtains MgIn
2O
4/ MgO compound substrate.The compound substrate of this kind structure is suitable for epitaxial growth of high quality GaN.
Prepare MgIn with magnetron sputtering experimental provision shown in Figure 1
2O
4The method of/MgO compound lining material is described as follows with preferred embodiment:
The MgO single crystalline substrate of polishing, cleaning is sent into magnetic control sputtering device, and the base vacuum pressure of instrument system is 2 * 10
-3Pa, the radio-frequency power scope is 100-250W, target is by the In of purity 〉=99.99%
2O
3Powder forms through the briquetting sintering, and target diameter is 85mm, thickness 3mm, and target is set to 300mm to the distance of substrate, the sputter high-purity argon gas of purity 〉=99.999%, ar pressure is 6.6 * 10
-2Pa, substrate are the MgO single-chip of twin polishing, and underlayer temperature is a room temperature, and thin film deposition speed is that (close 38 /min), adopt quartz crystal oscillator sheet monitoring deposition rate, film thickness is 500nm to 0.063nm/s.Then with resulting In
2O
3/ MgO sample is put into annealing furnace, is warming up to 1000 ℃, in order to suppress In
2O
3Volatilization, adopt the reaction atmosphere of rich In, In
2O
3With MgO solid phase reaction taking place at high temperature, has obtained MgIn
2O
4Cover layer obtains having the MgIn of different-thickness by the control annealing time
2O
4Cover layer recycles at last deionized water dissolving and falls responseless In
2O
3Layer, thus MgIn obtained
2O
4/ MgO compound substrate.The compound substrate of this kind structure is suitable for epitaxial growth of high quality GaN.
Claims (6)
1, a kind of conduction spinel structure MgIn
2O
4/ MgO compound lining material is characterized in that being provided with one deck MgIn at the MgO monocrystalline
2O
4, consist of MgIn
2O
4/ MgO compound substrate.
2, MgIn according to claim 1
2O
4The preparation method of/MgO compound lining material is characterized in that utilizing radio frequency magnetron sputtering method to prepare In in the MgO single crystalline substrate
2O
3Film then at high temperature, passes through In
2O
3With the solid phase reaction of MgO, form MgIn in the MgO single crystalline substrate
2O
4Cover layer.
3, MgIn according to claim 2
2O
4The preparation method of/MgO compound lining material is characterized in that described radiofrequency magnetron sputtering technology is to utilize Ar
+Behind electric field acceleration, become high energy incoming particle bump In
2O
3Target, the part momentum is passed to target atom, this target atom collides with other target atoms again, form cascade process, the target atom of some near surface obtains outwards enough momentum of motion in this cascade process, leave target and sputtered out, on the MgO single crystalline substrate of placing from the surperficial number centimeters of target, thereby adhere to, the accumulation deposit becomes In
2O
3Film.
4, MgIn according to claim 2
2O
4The preparation method of/MgO compound lining material is characterized in that it comprises following concrete steps:
＜1〉on the MgO single crystalline substrate, prepares In
2O
3Film: the MgO single crystalline substrate of will polish, cleaning is sent into magnetic control sputtering device, and the base vacuum pressure of instrument system is 2 * 10
-3Pa, the radio-frequency power scope is 100-250W, target is by the In of purity 〉=99.99%
2O
3Powder forms through the briquetting sintering, and target diameter is 85mm, thickness 3mm, and target is set to 300mm to the distance of substrate, the sputter high-purity argon gas of purity 〉=99.999%, ar pressure is 6.6 * 10
-2Pa, substrate are the MgO single-chip of twin polishing, and underlayer temperature is a room temperature, and thin film deposition speed is that (close 38 /min), adopt quartz crystal oscillator sheet monitoring deposition rate, film thickness is 500nm to 0.063nm/s.
＜2〉then with In obtained in the previous step
2O
3/ MgO sample is put into annealing furnace, is warming up to 700～1500 ℃, under the reaction atmosphere of rich In, makes In
2O
3With MgO solid phase reaction taking place at high temperature, has obtained MgIn
2O
4Cover layer obtains MgIn
2O
4/ MgO compound substrate.
5, MgIn according to claim 2
2O
4The preparation method of/MgO compound lining material is characterized in that described In
2O
3The purity of target is better than 99.99%.
6, MgIn according to claim 2
2O
4The preparation method of/MgO compound lining material is characterized in that described In
2O
3When with MgO solid phase reaction taking place, the optimum temperature in the annealing furnace is 1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031510817A CN1527412A (en) | 2003-09-19 | 2003-09-19 | Composite substrate material of conductive spinel structure MgIn2O4/MgO and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031510817A CN1527412A (en) | 2003-09-19 | 2003-09-19 | Composite substrate material of conductive spinel structure MgIn2O4/MgO and its prepn |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295747C (en) * | 2004-10-13 | 2007-01-17 | 中国科学院上海光学精密机械研究所 | Material with composite substrate of (Mg, Cd) In2O4/MgAl/204 and its prepn method |
| CN102962450A (en) * | 2012-12-12 | 2013-03-13 | 广汉川冶新材料有限责任公司 | Vacuum sintering method used in powder metallurgy process |
| WO2020223471A1 (en) * | 2019-04-30 | 2020-11-05 | Shell Oil Company | Devices containing conductive magnesium oxides |
-
2003
- 2003-09-19 CN CNA031510817A patent/CN1527412A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295747C (en) * | 2004-10-13 | 2007-01-17 | 中国科学院上海光学精密机械研究所 | Material with composite substrate of (Mg, Cd) In2O4/MgAl/204 and its prepn method |
| CN102962450A (en) * | 2012-12-12 | 2013-03-13 | 广汉川冶新材料有限责任公司 | Vacuum sintering method used in powder metallurgy process |
| WO2020223471A1 (en) * | 2019-04-30 | 2020-11-05 | Shell Oil Company | Devices containing conductive magnesium oxides |
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