CN100337336C - Zinc oxide homogeneous p-n junction material and method for making same - Google Patents
Zinc oxide homogeneous p-n junction material and method for making same Download PDFInfo
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- CN100337336C CN100337336C CNB2003101091391A CN200310109139A CN100337336C CN 100337336 C CN100337336 C CN 100337336C CN B2003101091391 A CNB2003101091391 A CN B2003101091391A CN 200310109139 A CN200310109139 A CN 200310109139A CN 100337336 C CN100337336 C CN 100337336C
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract 2
- 229960001296 zinc oxide Drugs 0.000 claims description 38
- 239000011701 zinc Substances 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 52
- 238000000889 atomisation Methods 0.000 abstract description 4
- 230000005693 optoelectronics Effects 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910002601 GaN Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 2
- 230000005678 Seebeck effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241001648319 Toronia toru Species 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 239000005357 flat glass Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用喷雾热解法，通过氮和铟的共掺杂，制备p-型氧化锌薄膜材料，通过掺杂铟制备低阻n-型氧化锌薄膜材料，从而制得ZnO同质结p-n结的方法。在该方法中，通过向先驱体溶液中添加适量的含氮和含铟掺杂剂，经超声雾化热解反应制备p-型氧化锌薄膜，通过向先驱体溶液中添加适量的铟掺杂剂，经超声雾化热解反应制备低阻n-型氧化锌薄膜。在不同的材料表面上，先后生长p-型(或n-型)和n-型(或p-型)ZnO薄膜即可制得ZnO同质结p-n结。通过控制先驱体溶液浓度及配比、衬底温度、成膜气氛及雾化气量可实现对制得ZnO同质结p-n结电学性能的控制，以满足制备氧化锌基发光二极管(LEDs)，激光二极管(LDs)等光电子器件方面的需要。该法工艺简单易行，成本低廉。
The invention relates to a spray pyrolysis method, through the co-doping of nitrogen and indium, to prepare p-type zinc oxide thin film material, and to prepare low-resistance n-type zinc oxide thin film material by doping indium, so as to obtain homogeneous ZnO The method of junction pn junction. In this method, a p-type zinc oxide film is prepared by ultrasonic atomization pyrolysis reaction by adding an appropriate amount of nitrogen-containing and indium-containing dopants to the precursor solution, and by adding an appropriate amount of indium-doped agent, the low-resistance n-type zinc oxide thin film was prepared by ultrasonic atomization pyrolysis reaction. On the surface of different materials, p-type (or n-type) and n-type (or p-type) ZnO films can be grown successively to obtain a ZnO homojunction pn junction. By controlling the concentration and proportion of the precursor solution, substrate temperature, film-forming atmosphere and atomization gas volume, the electrical properties of the ZnO homojunction pn junction can be controlled to meet the requirements of the preparation of zinc oxide-based light-emitting diodes (LEDs), laser Diodes (LDs) and other optoelectronic devices. The process of the method is simple and easy, and the cost is low.
Description
Affiliated field
The present invention relates to be used for Zinc oxide-base light-emitting diode (LEDs), zinc oxide homojunction p-n junction material of opto-electronic devices such as laser diode (LDs) and ultraviolet detector and preparation method thereof belongs to technical field of semiconductor.
Background technology
Zinc oxide is a kind of novel II-VI family wide bandgap compound semiconductor material.Energy gap 3.37eV under the room temperature, exciton binding energy is up to 60meV.Can at room temperature realize the ultraviolet stimulated emission relevant with exciton, this character is highly beneficial for development efficiency diode and ultraviolet wavelength Laser Devices.Therefore be expected to develop multiple luminescent devices such as ultraviolet, green glow, blue light.To replace gallium nitride blue light (450nm) luminescent device.In addition, as a kind of wide bandgap semiconductor materials, ZnO also has the performance more more superior than GaN aspect several following:
1. defective is few in the high-quality ZnO film, can obtain the high efficiency semiconductor device;
2. there is multiple substrate to be fit to deposition ZnO film, realization applied widely, as to help complex function;
3. can carry out wet-chemical treatment to ZnO film, be suitable for the manufacture craft of miniature components and parts;
4. China's zinc resource is relatively abundant, cheap, and the growth temperature of ZnO film generally is lower than 500 ℃, far below the growth temperature (1050 ℃) of GaN, and preparation easily.
5. zinc oxide material avirulence, pollution-free belongs to green material.
But owing to have many intrinsic alms giver's defectives (as oxygen room Vo and gap zinc Zni) in the zinc oxide, acceptor doping is produced the height auto-compensation, natural is the n N-type semiconductor N, be difficult to realize that the p type changes, thereby cause to make zinc oxide homojunction p-n junction structure, though can prepare zinc oxide heterogeneous knot p-n junction structure,, limit the Application and Development of Zinc oxide-base photoelectric device because the lattice match problem makes material character not ideal enough.Therefore, the realization of zinc oxide p-n knot is the key technology of Zinc oxide-base photoelectric device, also is the major subjects in the zinc oxide research always.
For preparation zinc oxide p-n knot at first needs to solve the preparation problem of p type ZnO film.Preparing p type ZnO film mainly adopts the method for doping recipient element to realize.Wherein nitrogen is to use maximum elements, has the most shallow acceptor level because theory analysis shows nitrogen in zinc oxide, realizes compensation and inhibition to alms giver's defective in the zinc oxide easily.But because nitrogen active relatively poor is difficult to into key with zinc, the displacement position that is difficult to be implemented in oxygen retains, and the repulsive interaction between N and the N is stronger, can't the higher concentration doping.Therefore, the poor repeatability of experiment, electric property is difficult to accurate control, can't satisfy practical requirement.Have only few report successfully to prepare zinc oxide homojunction p-n junction material, this research still is in the exploratory stage in the world.Adopt pulsed laser deposition on p-type GaAs substrate, to prepare As doping p-type ZnO film if any report by thermal diffusion, the Al Doped n-type of growing thereon again ZnO film, thus made zinc oxide homojunction p-n junction (J.Crystal Growth 219 (2000) 419).People such as Toru prepare the P doped p type ZnO thin film by the laser doping technology on the single crystal ZnO substrate, and have realized ZnO homojunction p-n junction structure (Appl.Phys.Lett.76 (2000) 3257).But the laser method apparatus expensive, system film cost height is difficult to realize the large tracts of land deposition.Be suitable for fundamental research, aspect practical application, still have many problems to need to solve.And the compatible difficulty of single crystal ZnO substrate or GaAs substrate with semiconductor technology.
Summary of the invention
The objective of the invention is to solve the difficulty that zinc oxide is difficult to realize effective p-n junction structure, provide a kind of simple for process, with low cost, the new method of processability excellent oxidation zinc p-n junction material is to satisfy the needs of preparation zno-based opto-electronic device.The realization of zinc oxide homojunction p-n junction material will further promote ZnO film at light-emitting diode (LEDs), the Application and Development of field of optoelectronic devices such as laser diode (LDs) and ultraviolet detector.
Implementation procedure of the present invention comprises two parts, i.e. the deposition of the deposition of p-type ZnO film and n-type ZnO film.To deposit p-type ZnO film earlier, depositing n-type ZnO film more thereon is that example illustrates this process below.Also can deposit n-type ZnO film earlier, deposit p-type ZnO film more thereon.
(1) deposition of p-type ZnO film
Precursor solution is the aqueous solution, and main solute is chosen as:
Preferably, the zinc source is zinc acetate (Zn (CH
3COO)
2) or zinc nitrate (Zn (NO
3)
2Or zinc chloride (ZnCl
2).
Preferably, Zn
2+The concentration of solution is 0.1～1moll
-1
The preferred N of doped chemical, In, wherein:
Preferably, the N source is ammonium acetate (CH
3COONH
4), ammoniacal liquor (NH
4OH), ammonium nitrate (NH
4NO
3).
Preferably, NH
4 +Concentration is 1～5moll
-1
Preferably, the In source is indium nitrate (In (NO
3)
3), inidum chloride (InCl
3), indium acetate (In (CH
3COO)
3),
Preferably, In
3+Concentration is 0.1～1moll
-1
Preferably, the precursor solution proportioning is Zn: N: In=1: (1-3): (0.03-0.25).
Precursor solution atomizes through ultrasonic ultrasonic delay line memory, and the gas after the atomizing enters film forming room through the gas-liquid separation pipe, is deposited as the p-ZnO film at the substrate surface that heats.Zinc-oxide film ground deposition rate depends on substrate type, underlayer temperature, gas flow, nozzle and substrate distance etc., wherein:
Preferably, substrate is monocrystalline silicon piece, sheet glass, sapphire sheet.
Preferably, underlayer temperature is controlled at 400-600 ℃.
Preferably, the atomized soln wear rate is 0.2～2ml/min.
Preferably, nozzle and substrate distance are 5～15cm.
Under this technology, the deposition rate of zinc-oxide film is 10～40nm/min, and the atomic concentration percentage of nitrogen is 2～8%, and the atomic concentration percentage of indium is 0.5～5%.Thickness 0.3～1 μ m of p-type ZnO film.Referring to Chinese patent " a kind of nitrogen and indium codope prepare the method for p-type zinc-oxide film " (application number: 03151096.5).
(2) deposition of n-type ZnO film
Precursor solution is the aqueous solution, and main solute is chosen as:
Preferably, the zinc source is zinc acetate (Zn (CH
3COO)
2) or zinc nitrate (Zn (NO
3)
2Or zinc chloride (ZnCl
2).
Preferably, Zn
2+The concentration of solution is 0.1～1moll
-1
The preferred In of doped chemical, wherein:
Preferably, the In source is indium nitrate (In (NO
3)
3), inidum chloride (InCl
3), indium acetate (In (CH
3COO)
3),
Preferably, In
3+Concentration is 0.1～1moll
-1
Preferably, the precursor solution proportioning is Zn: In=1: (0.03-0.25).
Precursor solution atomizes through ultrasonic ultrasonic delay line memory, and the gas after the atomizing enters film forming room through the gas-liquid separation pipe, is deposited as n-type ZnO film at heating p-ZnO film surface, promptly constitutes ZnO homojunction p-n junction structure.Zinc-oxide film ground deposition rate depends on underlayer temperature, gas flow, nozzle and substrate distance etc., wherein:
Preferably, underlayer temperature is controlled at 400-600 ℃.
Preferably, the atomized soln wear rate is 0.2～2ml/min.
Preferably, nozzle and substrate distance are 5～15cm.
Under this technology, the deposition rate of zinc-oxide film is 10～40nm/min, the atomic concentration percentage 0.5～5% of indium.The thickness of n-type ZnO film is 0.3～1 μ m.
The thickness of gained ZnO homojunction p-n junction is 0.6～2 μ m.
Description of drawings
Fig. 1 prepares the device schematic diagram of p type zinc-oxide film for spray pyrolysis.This device comprises ultrasonic ultrasonic delay line memory 1, atomizing cup 2, gas-liquid separation pipe 3, film forming room 4, substrate 5, substrate heater 6.
The section structure schematic diagram of Fig. 2 embodiment 1ZnO homojunction p-n junction
The I-V characteristic curve of Fig. 3 embodiment 1ZnO homojunction p-n junction
The I-V characteristic curve of Fig. 4 embodiment 2ZnO homojunction p-n junction
The section structure schematic diagram of Fig. 5 embodiment 3ZnO homojunction p-n junction
The I-V characteristic curve of Fig. 6 embodiment 3ZnO homojunction p-n junction
Embodiment
Further illustrating the concrete implementation process of the present invention and substantive distinguishing features and obvious improvement, but the present invention only is confined to embodiment by no means below by embodiment.
Embodiment 1:
Substrate adopts monocrystalline silicon piece Si (100).The precursor solution proportioning of p-type ZnO film: 0.5moll
-1Zn (CH
3COO)
28mL, 5moll
-1COONH
42mL, 1moll
-1In (NO
3)
30.5mL.Solvent all adopts deionized water.The precursor solution for preparing is poured in the ultrasonic atomization cup.Monocrystalline silicon piece Si (100), is put at once and is heated to 420 ℃ on the stone or metal plate for standing a stove on as a precaution against fire after 3 minutes with the hydrofluoric acid etch.After treating that substrate reaches design temperature, start ultrasonic ultrasonic delay line memory, as carrier gas, the precursor solution wear rate is 0.2ml/min with filtered air, and the gas after the atomizing enters glass film forming room through the gas-liquid separation pipe, and keeping nozzle is 6 centimetres to substrate distance.Film is more even will constantly adjust nozzle orientation in order to make.Stopped spraying in about 5 minutes, cover a part of film with hearth electrode, continue spraying stops p-type ZnO film after about 10 minutes deposition as the p-n junction test with silicon chip.Reduce to 400 ℃ 420 ℃ of insulations after 5 minutes.Continue to grow n-type ZnO film thereon.Atomizing cup is cleaned up and pours into the precursor solution of n-type ZnO film, proportioning is: 0.5moll
-1Zn (CH
3COO)
28mL, 1moll
-1In (NO
3)
30.2mL.Start ultrasonic ultrasonic delay line memory open type sprayed deposit, other Control Parameter is identical with the deposition process of p-type ZnO film.Stopped spraying in about 15 minutes.Reduce to room temperature 400 ℃ of insulations after 5 minutes, make ZnO homojunction p-n junction.
The N that grows under the above condition, In codope zinc-oxide film is reduced to room temperature through the Hall effect test shows, and conduction type is P type, i.e. hole conduction.Resistivity 5.1 * 10
-3Ω cm. carrier mobility 33.5cm
2V
-1s
-1. carrier concentration 3.69 * 10
19/ cm
3The conduction type of the zinc-oxide film that Seebeck effect test result conclusive evidence is grown is the P type.XPS (x-ray photoelectron spectroscopy) film chemical composition analysis result is: Zn 46.2%O 43.6%N 4.4%In 3.6%C 2.2%.In doping zinc-oxide film is reduced to room temperature through the Hall effect test shows, and conduction type is n type, i.e. electron conduction.Resistivity 1.09 * 10
-2Ω cm. carrier mobility 16.5cm
2V
-1s
-1. carrier concentration 3.45 * 10
19/ cm
3The conduction type of the zinc-oxide film that Seebeck effect test result conclusive evidence is grown is the n type.XPS (x-ray photoelectron spectroscopy) film chemical composition analysis result is: Zn 48.4%O 46.9%In 0.9%C3.8%.
The section structure schematic diagram of the ZnO homojunction p-n junction of growing under the above condition as shown in Figure 2.Gold electrode is used for the characteristic test of I-V, and test result such as Fig. 3 can find out the rectifying effect of p-n junction significantly, and have lower threshold voltage.
Embodiment 2:
The precursor solution proportioning of p-type ZnO film: 0.5moll
-1Zn (CH
3COO)
28mL, 5moll
-1COONH
42mL, 1moll
-1In (NO
3)
30.2mL.430 ℃ of depositing temperatures.The precursor solution proportioning of n-type ZnO film is: 0.5moll
-1Zn (CH
3COO)
28mL, 1moll
-1In (NO
3)
30.1mL.350 ℃ of depositing temperatures.Other parameter control is with embodiment one.
I-V characteristic curve test result such as Fig. 4 of the ZnO homojunction p-n junction of growing under the above condition can find out the rectifying effect of p-n junction significantly.
Embodiment 3:
Earlier on single crystalline Si (100) substrate, do hearth electrode, deposit ZnO homojunction p-n junction more thereon with the grow TiN layer of about 0.1 μ m of pulsed laser deposition (PLD) method.The precursor solution proportioning of p-type ZnO film: 0.5moll
-1Zn (CH
3COO)
28mL, 5moll
-1COONH
42mL, 1moll
-1In (NO
3)
30.6mL.430 ℃ of depositing temperatures.The precursor solution proportioning of n-type ZnO film is: 0.5moll
-1Zn (CH
3COO)
210mL, 1moll
-1In (NO
3)
30.1mL.400 ℃ of depositing temperatures.Other parameter control is with embodiment one.
The section structure schematic diagram of the ZnO homojunction p-n junction of growing under the above condition as shown in Figure 5.The characteristic test result of I-V such as Fig. 6 can find out the rectifying effect of p-n junction significantly, and have lower threshold voltage.
Claims (6)
1, a kind of zinc oxide homojunction p-n junction material is characterized in that comprising p-type ZnO film and n-type ZnO film, thickness 0.3～1 μ m of p-type ZnO film, and wherein the atomic concentration percentage of nitrogen is 2～8%, the atomic concentration percentage of indium is 0.5～5%; The thickness of n-type ZnO film is 0.3～1 μ m, the atomic concentration percentage 0.5～5% of indium.
2, a kind of method for preparing zinc oxide homojunction p-n junction material is characterized in that comprising the deposition of p-type ZnO film and the deposition of n-type ZnO film:
P-type ZnO film adopts solution spray pyrolysismethod deposition, comprise the preparation of precursor solution and the deposition of zinc-oxide film, Zn in the precursor solution: N: In=1: (1-3): (0.03-0.25), precursor solution is through ultrasonic atomizatio, gas after the atomizing enters film forming room by the gas-liquid separation pipe, is deposited as p-type zinc-oxide film in heated substrate surface pyrolysis; Underlayer temperature is controlled at 400-600 ℃;
N-type ZnO film adopts solution spray pyrolysismethod deposition, comprise the preparation of precursor solution and the deposition of zinc-oxide film, Zn in the precursor solution: In=1: (0.03-0.25), precursor solution is through ultrasonic atomizatio, gas after the atomizing enters film forming room by the gas-liquid separation pipe, is deposited as n-type zinc-oxide film in heated substrate surface pyrolysis; Underlayer temperature is controlled at 400-600 ℃.
3, by the described a kind of method for preparing zinc oxide homojunction p-n junction material of claim 2, it is characterized in that preparing the zinc source of adopting in p-type ZnO and the n-type ZnO film is zinc acetate (Zn (CH
3COO)
2) or zinc nitrate (Zn (NO
3)
2) or zinc chloride (ZnCl
2), Zn
2+Concentration be 0.1～1moll
-1
4,, it is characterized in that preparing in p-type ZnO and the n-type ZnO film that to adopt the indium source be indium nitrate (In (NO by the described a kind of method for preparing zinc oxide homojunction p-n junction material of claim 2
3)
3), inidum chloride (InCl
3), indium acetate (In (CH
3COO)
3), In
3+Concentration is 0.1～1moll
-1
5,, it is characterized in that preparing in the p-type ZnO film that to adopt nitrogenous source be ammonium acetate (CH by the described a kind of method for preparing zinc oxide homojunction p-n junction material of claim 2
3COONH
4), ammoniacal liquor (NH
4OH), ammonium nitrate (NH
4NO
3), NH
4 +Concentration is 1～5moll
-1
6, by the described a kind of method for preparing zinc oxide homojunction p-n junction material of claim 2, the atomized soln wear rate when it is characterized in that the zinc-oxide film deposition is 0.2～2ml/min, and the deposition rate of zinc-oxide film is 10～40nm/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101091391A CN100337336C (en) | 2003-12-05 | 2003-12-05 | Zinc oxide homogeneous p-n junction material and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101091391A CN100337336C (en) | 2003-12-05 | 2003-12-05 | Zinc oxide homogeneous p-n junction material and method for making same |
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| CN100437908C (en) * | 2004-12-03 | 2008-11-26 | 中国科学院上海硅酸盐研究所 | Process for preparing nitrigen-aluminium co-blended hole zinc oxide thin film material |
| JP3945782B2 (en) * | 2005-09-06 | 2007-07-18 | シチズン東北株式会社 | Semiconductor light emitting device and manufacturing method thereof |
| CN100355657C (en) * | 2005-09-29 | 2007-12-19 | 江苏大学 | Method and device for in situ preparing zinc oxide nanometer crystal using coaxial oxygen transporting laser |
| CN101921986A (en) * | 2010-07-16 | 2010-12-22 | 北京工业大学 | A kind of zinc oxide doped homogeneous PN junction and its preparation method |
| DE112011103246B4 (en) | 2011-09-29 | 2021-09-23 | Beijing Yuji Science And Technology Co. Ltd | Nitride phosphors |
| CN102593242A (en) * | 2012-03-22 | 2012-07-18 | 中国科学院上海技术物理研究所 | Preparation method of wide-band thin-film photodetector with Pt/Ti/SiO2/Si substrate |
| CN103074683B (en) * | 2013-01-25 | 2015-03-11 | 合肥工业大学 | Coaxial homogeneous ZnO pn junction nanorod and preparation method thereof |
| CN103178444B (en) * | 2013-02-28 | 2015-04-01 | 溧阳市宏达电机有限公司 | Laser diode |
| CN104846335B (en) * | 2015-05-28 | 2017-06-23 | 深圳大学 | A kind of N-shaped cuprous oxide film and preparation method thereof |
| CN110364592B (en) * | 2018-04-10 | 2021-09-17 | Tcl科技集团股份有限公司 | Zinc oxide homojunction and preparation method thereof |
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| JP2002105625A (en) * | 2000-09-27 | 2002-04-10 | Japan Science & Technology Corp | Method for manufacturing low resistivity p-type zinc oxide thin film |
| US6624441B2 (en) * | 2002-02-07 | 2003-09-23 | Eagle-Picher Technologies, Llc | Homoepitaxial layers of p-type zinc oxide and the fabrication thereof |
| US6638846B2 (en) * | 2000-09-13 | 2003-10-28 | National Institute Of Advanced Industrial Science And Technology And Rohm Co., Ltd. | Method of growing p-type ZnO based oxide semiconductor layer and method of manufacturing semiconductor light emitting device |
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| US6638846B2 (en) * | 2000-09-13 | 2003-10-28 | National Institute Of Advanced Industrial Science And Technology And Rohm Co., Ltd. | Method of growing p-type ZnO based oxide semiconductor layer and method of manufacturing semiconductor light emitting device |
| JP2002105625A (en) * | 2000-09-27 | 2002-04-10 | Japan Science & Technology Corp | Method for manufacturing low resistivity p-type zinc oxide thin film |
| US6624441B2 (en) * | 2002-02-07 | 2003-09-23 | Eagle-Picher Technologies, Llc | Homoepitaxial layers of p-type zinc oxide and the fabrication thereof |
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