CN101921986A - Zinc oxide doped PN homojunction and preparation method thereof - Google Patents
Zinc oxide doped PN homojunction and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a zinc oxide (ZnO) doped PN homojunction and a preparation method thereof. A ZnO cobalt doped film is used as a P-type junction; a ZnO indium-gallium (In-Ga) doped film is used as an N-type junction; the P-type cobalt doped ZnO film is attached to a substrate; the N-type In-Ga doped ZnO film is attached to the P-type cobalt doped ZnO film; and part of the P-type cobalt doped ZnO film is covered by the N-type ZnO In-Ga doped film. The preparation method adopts a pulsed laser deposition method and comprises the following steps: preparing Zn 0.9 Co 0.1 O and In 0.8 Ga 0.1 Zn 0.1 O ceramic target materials by a solid reaction sintering method; and separately preparing the P-type cobalt doped ZnO film and the N-type In-Ga doped ZnO film by the pulsed laser deposition method so as to form the p-n homojunction. The invention has the advantages of good crystallization quality and smooth surface and a nanometer structure.
Description
Technical field
The present invention relates to a kind of pulsed laser deposition and prepare zinc oxide PN homojunction and preparation method thereof.
Background technology
ZnO is a kind of novel II-VI family direct band gap broad stopband photoelectric semiconductor material, and people start from the report of ZnO light at room temperature pumping Ultra-Violet Laser emission in 1997 and self-assembly resonator cavity phenomenon to the very big concern of its photoelectric properties.In fact, ZnO and GaN not only have identical crystalline structure, close lattice parameter and energy gap, and ZnO has than higher fusing point of GaN and bigger exciton bind energy, are easier to realize the high-level efficiency Laser emission under room temperature or the higher temperature.In addition, ZnO also has the thermostability height, anti-particle radiation damage is strong, epitaxial temperature is low, film forming properties is good, can carry out wet etching, easily obtain the big area single crystalline substrate, abundant raw material, advantage such as nontoxic.Therefore, the equivalent material that ZnO can be used as GaN is applied to short-wavelength light electrical part field, as photodiode (LEDs), laser apparatus (LDs), ultraviolet detector etc.
At present, the research of ZnO p-n junction still is in the primary stage, has only the electricity of having realized ZnO to inject to swash and penetrates, and could realize the practicability that ZnO is real.Hindering the ZnO p-n junction is can't effectively mix obtaining p type ZnO film in one of topmost factor of aspect widespread uses such as photoelectricity, thereby realizes basic p-n junction structure in semi-conductor and the photoelectric device.For the p-ZnO film, owing to have many intrinsic alms giver's defectives among the ZnO, as zinc gap Zni and oxygen room Vo, its energy level lays respectively at 0.05eV and 0.3eV place at the bottom of the conduction band, can be to being subjected to the stronger auto-compensation of main product life.In addition, the acceptor level among the ZnO is generally very dark, and the hole is difficult for entering valence band by thermal excitation, and the solid solubility of acceptor doping is also very low, therefore is difficult to realize the transformation of p type.For the n-ZnO film, realize that the n type is easy, but the ZnO doping that has high mobility and room temperature preparation condition simultaneously is difficult for.
Summary of the invention
The purpose of this invention is to provide a kind of Zinc oxide doped Homojeneous p-n Junction and preparation method thereof.
A kind of Zinc oxide doped PN homojunction of the present invention, mixing cobalt thin film by ZnO ties as the P type, ZnO mixes indium gallium film and ties as the N type, the ZnO of P type mixes cobalt thin film attached on the substrate base, N type ZnO mixes the ZnO that indium gallium film is attached to the P type and mixes on the cobalt thin film, the ZnO of P type mixes the part of cobalt thin film and is mixed the covering of indium gallium film by N type ZnO, form PN junction at the intermediary interface, form the PN junction of level up and down, select mask method to prepare PN junction contacts electrode surface in the preparation process, as electrode, the ZnO that is welded in the P type respectively mixes the cobalt thin film surface and N type ZnO mixes indium gallium film surface with the In metal.
It is Zn that above-mentioned ZnO mixes cobalt thin film
0.9Co
0.1The O film, it is In that N type ZnO mixes indium gallium film
0.8Ga
0.1Zn
0.1The O film.
Zinc oxide doped Homojeneous p-n Junction of the present invention prepares by pulsed laser deposition, adopts following technical scheme to realize: adopt the solid reaction sintering process to prepare Zn earlier
0.9Co
0.1O and In
0.8Ga
0.1Zn
0.1The O ceramic target, (Pulse Laser deposition PLD) prepares P type cobalt-doped zinc oxide film and N type respectively and mixes indium gallium zinc-oxide film, forms Homojeneous p-n Junction to adopt pulsed laser deposition again.
Concrete steps are as follows:
1) preparation Zn
0.9Co
0.1The O ceramic target:
With the ZnO of purity 〉=99.99% and the Co of purity 〉=99.99%
2O
3By Zn: Co atomic molar ratio is after mixing at 9: 1 and grinding 2～10 hours, in 850～1200 ℃ of insulations 6～12 hours, to be cooled to room temperature, behind the regrinding 2～10 hours, be pressed into the solid target, the solid target in 850～1200 ℃ of insulations 6～12 hours, is obtained Zn
0.9Co
0.1The O ceramic target;
2) growing P-type cobalt-doped zinc oxide film:
With the Zn for preparing in the step 1)
0.9Co
0.1The O pottery is a target, is substrate with sapphire, single crystalline Si or silica glass, adopts the pulsed deposition legal system to be equipped with P type cobalt-doped zinc oxide film, and vacuum chamber is evacuated to 2.5 * 10
-4～2.5 * 10
-5Behind the Pa, obstructed any atmosphere, regulate laser power to 200～600mw, target and substrate vertically are placed on the plumage brightness sputter direction, regulate target-substrate distance to 4-5cm, while rotary target material and substrate, and adjust spot size and the position makes the complete covering substrate of plumage brightness front end according to plumage brightness size, with guarantee the film surface that plated even, substrate is heated to 700～800 ℃, open baffle plate, deposit 20～60 minutes.
3) preparation In
0.8Ga
0.1Zn
0.1The O ceramic target:
In with purity 〉=99.99%
2O
3, purity 〉=99.99% Ga
2O
3And the ZnO powder of purity 〉=99.99%, in 8: 1: 1 In: Ga: Zn atomic molar ratio weighing powder, in mortar, carry out mixing and grinding, under atmospheric air atmosphere, carry out high temperature sintering 6～14h, sintering temperature is 1000～1400 ℃; Powder after the presintering after milled processed, is pressed, obtains expecting embryo, forming pressure is 8～10MPa, the time 2～4min that keep-ups pressure, and high temperature sintering 6～14h once more, sintering temperature is 1000～1400 ℃, makes In
0.8Ga
0.1Zn
0.1The O target;
4) growing n-type is mixed indium gallium zinc-oxide film:
With In
0.8Ga
0.1Zn
0.1Pack into after the O target material surface cleans in the vacuum chamber, vacuum chamber is vacuumized, when vacuum tightness reaches 10
-3When Pa is above,, make oxygen partial pressure remain on 3 * 10 simultaneously to the vacuum chamber aerating oxygen
-1Under～15Pa the pressure.With the ultraviolet pulse laser is that light source deposits, and half that utilize simultaneously that mask will plate P type film blocked, and has only half film to be exposed under the plasma plume brightness, target and substrate carried out rotation, target-substrate distance 30～50mm; Adjust the ultraviolet pulse laser output rating simultaneously at 200～600mw, make nuclear shape plumage brightness end touch substrate just, In grows under the room temperature underlayer temperature
0.8Ga
0.1Zn
0.1O film, depositing time are 10～120min.
The beneficial effect that the present invention has:
The present invention adopts pulsed laser deposition with the even ZnO that mixes of different ions, under the prerequisite of not disruptive oxidation zinc structure, prepare nanostructure, good, the ganoid homogeneity zinc oxide semi-conductor of crystalline quality p-n junction, created the good premise condition for next step preparation has zno-based photodiode, transistor, photodetector and solar cell application.
Description of drawings
Fig. 1 is the zinc oxide PN homojunction structural profile synoptic diagram of embodiment 1 preparation.
Fig. 2 is the zinc oxide PN homojunction rectification characteristic curve test pattern of embodiment 2 preparations.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
A kind of Zinc oxide doped PN homojunction, see Fig. 1, mixing cobalt thin film by ZnO ties as the P type, ZnO mixes indium gallium film and ties as the N type, the ZnO of P type mixes cobalt thin film attached on the substrate base, N type ZnO mixes the ZnO that indium gallium film is attached to the P type and mixes on the cobalt thin film, the ZnO of P type mixes the part of cobalt thin film and is mixed the covering of indium gallium film by N type ZnO, form PN junction at the intermediary interface, form the PN junction of level up and down, select mask method to prepare PN junction contacts electrode surface in the preparation process, as electrode, the ZnO that is welded in the P type respectively mixes the cobalt thin film surface and N type ZnO mixes indium gallium film surface with the In metal.
It is Zn that above-mentioned ZnO mixes cobalt thin film
0.9Co
0.1The O film, it is In that N type ZnO mixes indium gallium film
0.8Ga
0.1Zn
0.1The O film.
1) preparation Zn
0.9Co
0.1The O ceramic target:
With 14.2621g purity is that 99.99% ZnO and 1.5297g purity are 99.99% Co
2O
3(mol ratio is 0.9: 0.05) put into the agate beveller and ground after 3 hours, place the corundum sintering container in 5 hours, to be warming up to 1200 ℃ and be incubated 6 hours, be cooled to room temperature, in the agate beveller, grind after 4 hours once more, press target drone (12MPa suppressed 3 minutes down) to be pressed into the circular target of solid that diameter is 30mm through hydraulic pressure, the circular target of solid is put into tube furnace in 1200 ℃ of insulations 11 hours, obtain purity and be 99.99% Zn
0.9Co
0.1The O ceramic target;
2) preparation P type cobalt-doped zinc oxide film:
With the Zn for preparing in the step 1)
0.9Co
0.1The O pottery is a target, with Al
2O
3Monocrystalline is a substrate, adopts the pulsed deposition legal system to be equipped with P type cobalt-doped zinc oxide film, and vacuum chamber is evacuated to 2.5 * 10
-4Pa, obstructed any atmosphere, adopt and transfer Q Nd:YAG pulsed laser, optical maser wavelength 355nm, repetition rate 10Hz, pulsewidth 10ns, by plasma plume brightness size and shape, regulate lens, target position, target-substrate distance to 5cm, laser power is to 420mw, and then the adjustment light path, facula position and spot size, make the complete covering substrate of plumage plasma brightness front end, the closure molecule pump, vacustat is to 0.9Pa by the time, substrate is heated to 800 ℃, and allow laser to target surface bombardment 3 minutes, and open baffle plate, deposit 30 minutes.
3) preparation In
0.8Ga
0.1Zn
0.1The O ceramic target
With 11.372g purity 99.99% In
2O
3, 1.9194g purity is that 99.999% Ga203 and 4.1672g purity are 99.99% ZnO powder (mol ratio is 8: 1: 1), adopts analytical balance weighing powder, and powder put into carries out mixing and grinding in the agate mortar.Powder through refinement places tube furnace sintering 6h, and sintering temperature is 1000 ℃.The powder of presintering is pulverized once more and ground, adopt dry pressure formed technology, powder is suppressed through the hydraulic pressure tabletting machine, obtains the cake moulding mixture base of diameter 30mm, thickness 5mm.Forming pressure is 10MPa, and time 2min keep-ups pressure.Material base places tube furnace sintering 6h once more then, and sintering temperature is 1400 ℃, makes the InGaZnO target.
4) preparation N type indium gallium zinc oxygen film
In
0.8Ga
0.1Zn
0.1The O growth for Thin Film adopts pulsed laser deposition to carry out.Use the triple-frequency harmonics (wavelength is 355nm) of Nd:YAG pulsed laser, substrate is a sapphire, and the P type cobalt-doped zinc oxide film that utilizes mask to have prepared on substrate blocks half, target-substrate distance 50mm.At first, open the mechanical pump of vacuum system, vacuum chamber is vacuumized.When vacuum tightness reaches 0～5Pa, open molecular pump, proceed vacuum pumping.Then, when the base vacuum degree reached 2.5 * 10-4Pa, the closure molecule pump was opened mechanical pump, and simultaneously to the vacuum chamber aerating oxygen, made oxygen partial pressure remain on 5.0Pa.During deposition, average laser power is 400mW before focusing on, and target and substrate carry out rotation simultaneously, and substrate temperature is room temperature (RT), and depositing time is 30min.
1) with the step 1) among the embodiment 1;
2) make the thickness of P type film increase except that depositing time being extended to 40 minutes and regulate spot size and position, other are operated all with the step 2 among the embodiment 1);
3) with the step 3) among the embodiment 1;
4) with the step 4) among the embodiment 1.
The Hall effect detected result of the p-n junction film of table 1 embodiment 1-2 preparation.
Claims (3)
1. Zinc oxide doped PN homojunction, it is characterized in that, mixing cobalt thin film by ZnO ties as the P type, ZnO mixes indium gallium film and ties as the N type, the ZnO of P type mixes cobalt thin film on attached to substrate base, N type ZnO mixes the ZnO that indium gallium film is attached to the P type and mixes on the cobalt thin film, and the part that the ZnO of P type mixes cobalt thin film is mixed indium gallium film by N type ZnO and covered, and forms PN junction at the intermediary interface;
It is Zn that above-mentioned ZnO mixes cobalt thin film
0.9Co
0.1The O film, it is In that N type ZnO mixes indium gallium film
0.8Ga
0.1Zn
0.1The O film.
2. a kind of Zinc oxide doped PN homojunction of claim 1 is characterized in that, the ZnO that metal electrode In is welded in the P type respectively mixes the cobalt thin film surface and N type ZnO mixes indium gallium film surface.
3. the preparation method of a kind of Zinc oxide doped PN homojunction of claim 1 is characterized in that, may further comprise the steps:
1) preparation Zn
0.9Co
0.1The O ceramic target:
With ZnO and Co
2O
3By Zn: after the Co atomic molar mixed than 9: 1 and grinds 2～10 hours,, be cooled to room temperature in 850～1200 ℃ of insulations 6～12 hours, behind the regrinding 2～10 hours, be pressed into the solid target, the solid target in 850～1200 ℃ of insulations 6～12 hours, is obtained Zn
0.9Co
0.1The O ceramic target;
2) growing P-type cobalt-doped zinc oxide film:
With the Zn for preparing in the step 1)
0.9Co
0.1The O pottery is a target, is substrate with sapphire, single crystalline Si or silica glass, adopts the pulsed deposition legal system to be equipped with P type cobalt-doped zinc oxide film, and vacuum chamber is evacuated to 2.5 * 10
-4～2.5 * 10
-5Behind the Pa, regulate laser power to 200～600mw, target and substrate vertically are placed on the plumage brightness sputter direction, regulate target-substrate distance to 4-5cm, rotary target material and substrate make the complete covering substrate of plumage brightness front end simultaneously, substrate is heated to 700～800 ℃, deposits 20～60 minutes.
3) preparation In
0.8Ga
0.1Zn
0.1The O ceramic target:
With In
2O
3, Ga
2O
3And ZnO powder, in 8: 1: 1 In: Ga: Zn atomic molar ratio weighing powder, in mortar, carry out mixing and grinding, under atmospheric air atmosphere, carry out high temperature sintering 6～14h, sintering temperature is 1000～1400 ℃; Powder after the presintering after milled processed, is pressed, obtains expecting embryo, forming pressure is 8～10MPa, the time 2～4min that keep-ups pressure, and high temperature sintering 6～14h once more, sintering temperature is 1000～1400 ℃, makes In
0.8Ga
0.1Zn
0.1The O target;
4) growing n-type is mixed indium gallium zinc-oxide film:
With In
0.8Ga
0.1Zn
0.1Pack into after the O target material surface cleans in the vacuum chamber, vacuum chamber is vacuumized, when vacuum tightness reaches 10
-3When Pa is above,, make oxygen partial pressure remain on 3 * 10 simultaneously to the vacuum chamber aerating oxygen
-1Under～15Pa the pressure, be that light source deposits with the ultraviolet pulse laser, half that utilize simultaneously that mask will plate P type film blocked, and has only half film to be exposed under the plasma plume brightness, target and substrate carried out rotation, target-substrate distance 30～50mm; Adjust the ultraviolet pulse laser output rating simultaneously at 200～600mw, make nuclear shape plumage brightness end touch substrate just, In grows under the room temperature underlayer temperature
0.8Ga
0.1Zn
0.1O film, depositing time are 10～120min.
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Cited By (5)
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| CN104846335A (en) * | 2015-05-28 | 2015-08-19 | 深圳大学 | n-shaped cuprous oxide film and preparation method thereof |
| CN108914065A (en) * | 2018-08-01 | 2018-11-30 | 研创应用材料（赣州）股份有限公司 | A kind of novel RPD polynary conductive oxide material and preparation method thereof |
| CN112201711A (en) * | 2020-09-10 | 2021-01-08 | 湖北大学 | ZnO-based homojunction self-driven ultraviolet photoelectric detector and preparation method thereof |
| CN117832333A (en) * | 2024-03-05 | 2024-04-05 | 龙焱能源科技（杭州）有限公司 | Cadmium telluride thin film battery and preparation method thereof |
| CN117832333B (en) * | 2024-03-05 | 2024-05-31 | 龙焱能源科技（杭州）有限公司 | Cadmium telluride thin film battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112201711A (en) * | 2020-09-10 | 2021-01-08 | 湖北大学 | ZnO-based homojunction self-driven ultraviolet photoelectric detector and preparation method thereof |
| CN117832333A (en) * | 2024-03-05 | 2024-04-05 | 龙焱能源科技（杭州）有限公司 | Cadmium telluride thin film battery and preparation method thereof |
| CN117832333B (en) * | 2024-03-05 | 2024-05-31 | 龙焱能源科技（杭州）有限公司 | Cadmium telluride thin film battery and preparation method thereof |
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Open date: 20101222 |