CN1527361A - N and In codoping process in preparing hole type zinc oxide film - Google Patents
N and In codoping process in preparing hole type zinc oxide film Download PDFInfo
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- CN1527361A CN1527361A CNA031510965A CN03151096A CN1527361A CN 1527361 A CN1527361 A CN 1527361A CN A031510965 A CNA031510965 A CN A031510965A CN 03151096 A CN03151096 A CN 03151096A CN 1527361 A CN1527361 A CN 1527361A
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- oxide film
- zinc
- zinc oxide
- precursor solution
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Abstract
The present invention relates to the spraying and thermolysis process of codoping N and In to prepare hole type zinc oxide film material. N and In containing doping agent is added into precursor solution; and through ultrasonic atomizing and thermolysis reaction, hole type zinc oxide film with the Zn ion, NH ion and In ion in the ratio of 1 to 1-3 to 0.05-0.2 is prepared on the surface of different materials. The substrate material is monocrystalline silicon chip, glass chip or sapphire; and the substrate temperature is controlled in 400-600 deg.c. The concentration and composition of the precursor solution, substrate temperature, filming atmosphere and atomizing gas flow rate are controlled to control the electric performance and carrier density of the hole type zinc oxide film, so as to meet the requirement of preparing zinc oxide semiconductor material, zinc oxide-base LEDs, LDs and other photoelectronic devices. The present invention has simple and practical technological process and low cost.
Description
Technical field
The present invention relates to be used for Zinc oxide-base light-emitting diode (LEDs), the preparation method of cavity type (p-type) Zinc oxide film material of opto-electronic devices such as laser diode (LDs) and ultraviolet detector.Belong 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.Be expected to develop multiple luminescent devices such as ultraviolet, green glow, blue light.To replace gallium nitride blue light (450nm) luminescent device.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, be generally the n N-type semiconductor N, and be difficult to realize that the p type changes, thereby cause to make zinc oxide p-n junction structure, limited the Application and Development of Zinc oxide-base photoelectric device.Therefore, the realization of ZnO film p type doping is the key technology of Zinc oxide-base photoelectric device.
Prepare that method that the p-ZnO film mainly adopts the doping recipient element realizes.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.At present, has only seldom this respect to study successfully to realize the report that the p type changes people such as (, Jpn.J.Appl.Phys.36, L1453 (1997) and Ji Zhenguo etc., Chinese patent CN 1377992A) K.Minegishi.This is because nitrogen active relatively poor is difficult to into key with zinc, and the displacement position that is difficult to be implemented in oxygen retains, and the repulsive interaction between N and the N is stronger, the problem of aspect.The nitrogen commonly used at present and the experiment of IIIA family element codope mainly on pulsed laser deposition (PLD) equipment, realize by change gas source kind.Wherein by Ga, and the N codope (people such as H.Tabata, Physica B, 2001,308-310:993-998) successfully prepared the p-ZnO film, film resiativity is 0.5ohm-cm, acceptor concentration can reach 5 * 10
19Cm
-3But the pulsed laser deposition 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.
Summary of the invention
The objective of the invention is to solve the difficulty that is difficult to realize effective acceptor doping in the zinc-oxide film, the new method that provides a kind of nitrogen and indium codope to prepare p type zinc-oxide film is to satisfy the needs of preparation zinc oxide p-n knot material and zno-based opto-electronic device.Has advantage simple for process, with low cost.
The present invention adopts the solution spray pyrolysismethod to realize that its process comprises two parts, i.e. the deposition of precursor solution preparation and zinc-oxide film.
(1) precursor solution is the aqueous solution, and main solute is chosen as:
(1) the zinc source is zinc acetate (Zn (CH
3COO)
2) or zinc nitrate (Zn (NO
3)
2Or zinc chloride (ZnCl
2).
(2) Zn
2+The concentration of solution is 0.1～1M.
Doped chemical is selected N, 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 1～5M;
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 0.1～1M;
Preferably, precursor solution gram molecule proportioning is Zn
2+: NH
4 +: In
3+=1: (1-3): (0.05-0.2).
(2) deposition of zinc-oxide film
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.The deposition rate of zinc-oxide film depends on substrate type, underlayer temperature, gas flow, nozzle and substrate distance etc., wherein:
Substrate is monocrystalline silicon piece, quartz glass plate or sapphire sheet.
Underlayer temperature is controlled at 400-600 ℃.
Carrier gas is a filtered air.
The atomized soln wear rate is 0.2～2ml/min.
Nozzle and substrate distance are 5～15cm.
Under this technology, the deposition rate of zinc-oxide film is 10～40nm/min, and the concentration of nitrogen is 2～10%, and the concentration of indium is 1～10%.
Can realize control by control precursor solution concentration and proportioning, underlayer temperature, film forming atmosphere and atomizing tolerance to p-type zinc-oxide film electric property and carrier concentration, to satisfy preparation zinc oxide p-n knot material and Zinc oxide-base light-emitting diode (LEDs), the needs of laser diode opto-electronic device aspects such as (LDs).This method is simple for process, and is with low cost.
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.
Fig. 2 is N, the XPS collection of illustrative plates of N in the In codope ZnO film.Abscissa is binding energy (eV), and ordinate is intensity (a.u.).
Fig. 3 is N, the XPS collection of illustrative plates of In in the In codope ZnO film.Abscissa is binding energy (eV), and ordinate is intensity (a.u.).
Fig. 4 is N, the SEM collection of illustrative plates (surface) of In codope ZnO film.
Fig. 5 is N, the SEM collection of illustrative plates (section) of In codope ZnO film.
Fig. 6 is N, the XRD figure spectrum of In codope ZnO film.Abscissa be scan angle (°), ordinate is intensity (a.u.).
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 (100) face monocrystalline silicon piece.Precursor solution proportioning: 0.5M Zn (CH
3COO)
28mL, 5M COONH
42mL, 1M In (NO
3)
31mL.Solvent all adopts deionized water.Institute joins that the gram molecule proportioning is Zn in the precursor solution
2+: NH
4 +: In
3+=1: 2.5: 0.25.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 15 minutes, reduce to room temperature after 5 minutes 420 ℃ of insulations.
The zinc-oxide film of growing under the above condition is through the Hall effect test shows, and conduction type is P type, i.e. hole conduction.Resistivity 2.2 * 10
-2Ω cm.Carrier mobility 17.4cm
2V
-1s
-1Carrier concentration 1.63 * 10
19/ cm
3The conduction type of the zinc-oxide film that Seebeck effect test result conclusive evidence is grown is the P type.
The zinc-oxide film of growing under the above condition shows that through X-ray photoelectron spectroscopic analysis each element atomic ratio is in the film: zinc 50.4%, oxygen 39.9%, indium 4.2%, nitrogen 5.5%.The XPS spectrum figure of nitrogen and indium such as accompanying drawing 2 and accompanying drawing 3.
Embodiment 2:
Precursor solution proportioning: 0.5M Zn (CH
3COO)
28mL, 5M COONH
42.4mL, 1M In (NO
3)
30.4mL.Institute joins that the gram molecule proportioning is Zn in the precursor solution
2+: NH
4 +: In
3+=1: 3: 0.1.Underlayer temperature is 450 ℃.Other condition is with example 1.The zinc-oxide film of growth is through the Hall effect test shows, and conduction type is P type, i.e. hole conduction.Resistivity 2.66 * 10
-2Ω cm.Carrier mobility 10.5cm
2V
-1s
-1Carrier concentration 2.23 * 10
19/ cm
3
The zinc-oxide film of growing under the above condition is through the field emission scanning electron microscope analysis, surface and cross-section morphology such as Fig. 4 and Fig. 5.
Embodiment 3:
Substrate is selected quartz glass plate for use.Precursor solution proportioning: 0.5M Zn (CH
3COO)
28mL, 5MCOONH
42.4mL, 1M In (NO
3)
30.6mL.Institute joins that the gram molecule proportioning is Zn in the precursor solution
2+: NH
4 +: In
3+=1: 3: 0.15.Underlayer temperature is 500 ℃.Other condition is with example 1.The zinc-oxide film of growth is through the Hall effect test shows, and conduction type is P type, i.e. hole conduction.Resistivity 1.09 * 10
-2Ω cm.Carrier mobility 16.5cm
2V
-1s
-1Carrier concentration 3.45 * 10
19/ cm
3
The zinc-oxide film of growing under the above condition is through X-ray diffraction analysis, and XRD figure is composed as Fig. 6.
Claims (5)
1. nitrogen and phosphide element codope prepare the method for p-type zinc-oxide film, it is characterized in that adopting the solution spray pyrolysismethod, it is characterized in that comprising the preparation of precursor solution and two processes of deposition of zinc-oxide film, Zn in the precursor solution
2+: NH
4 +: In
3+=1: 1-3: 0.05-0.2, precursor solution is through ultrasonic atomizatio, and the gas after the atomizing enters film forming room via 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 ℃, and substrate can be selected monocrystalline silicon piece, sheet glass or sapphire.
2. prepare the method for p-type zinc-oxide film by described a kind of nitrogen of claim 1 and phosphide element codope, it is characterized in that the zinc source is Zn (CH in the precursor solution
3COO)
2, Zn (NO
3)
2Or ZnCl
2In a kind of; Zn
2+Solution concentration is 0.1-1M.
3. prepare the method for p-type zinc-oxide film by described a kind of nitrogen of claim 1 and phosphide element codope, it is characterized in that nitrogenous source is CH in the precursor solution
3COONH
4, NH
4OH or NH
4NO
3In a kind of, NH
4+Solution concentration is 1-5M.
4. prepare the method for p-type zinc-oxide film by described a kind of nitrogen of claim 1 and phosphide element codope, it is characterized in that the indium source is In (NO in the precursor solution
3)
3, InCl
3Or In (CHCOO)
3In a kind of, In
3+Solution concentration is 0.1-1M.
5. the method for preparing p-type zinc-oxide film by described a kind of nitrogen of claim 1 and phosphide element codope, the atomized soln wear rate is 0.2-2ml/min when it is characterized in that the zinc-oxide film deposition, film deposition rate is 10-40nm/min, and the concentration of nitrogen is 2-10%, and the concentration of indium is 1-10%.
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|---|---|---|---|
| CN 03151096 CN1291453C (en) | 2003-09-19 | 2003-09-19 | N and In codoping process in preparing hole type zinc oxide film |
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|---|---|---|---|
| CN 03151096 CN1291453C (en) | 2003-09-19 | 2003-09-19 | N and In codoping process in preparing hole type zinc oxide film |
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|---|---|
| CN1527361A true CN1527361A (en) | 2004-09-08 |
| CN1291453C CN1291453C (en) | 2006-12-20 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431970C (en) * | 2005-10-27 | 2008-11-12 | 江苏大学 | Method and device for preparing zinc oxide nano-crystal by microwave induced adulterant oxidation |
| 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 |
| CN103055873A (en) * | 2013-01-04 | 2013-04-24 | 华东理工大学 | Composite photocatalyst membrane material with hierarchical pore structure and preparation method thereof |
| CN105349953A (en) * | 2015-10-12 | 2016-02-24 | 哈尔滨工业大学 | Method for preparing p-type zinc oxide from Zn3N2:elements of group three through thermal oxidation |
| CN106591913A (en) * | 2015-10-20 | 2017-04-26 | 神华集团有限责任公司 | Zinc oxide nanopillar array material and electrochemical deposition method for controlling density and optical bandgap of zinc oxide nanopillar arrays |
-
2003
- 2003-09-19 CN CN 03151096 patent/CN1291453C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN100431970C (en) * | 2005-10-27 | 2008-11-12 | 江苏大学 | Method and device for preparing zinc oxide nano-crystal by microwave induced adulterant oxidation |
| CN103055873A (en) * | 2013-01-04 | 2013-04-24 | 华东理工大学 | Composite photocatalyst membrane material with hierarchical pore structure and preparation method thereof |
| CN103055873B (en) * | 2013-01-04 | 2015-04-08 | 华东理工大学 | Composite photocatalyst membrane material with hierarchical pore structure and preparation method thereof |
| CN105349953A (en) * | 2015-10-12 | 2016-02-24 | 哈尔滨工业大学 | Method for preparing p-type zinc oxide from Zn3N2:elements of group three through thermal oxidation |
| CN105349953B (en) * | 2015-10-12 | 2018-07-03 | 哈尔滨工业大学 | Thermal oxide Zn3N2：The method that group-III element prepares p-type zinc oxide |
| CN106591913A (en) * | 2015-10-20 | 2017-04-26 | 神华集团有限责任公司 | Zinc oxide nanopillar array material and electrochemical deposition method for controlling density and optical bandgap of zinc oxide nanopillar arrays |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1291453C (en) | 2006-12-20 |
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