CN100437908C - Process for preparing nitrigen-aluminium co-blended hole zinc oxide thin film material - Google Patents
Process for preparing nitrigen-aluminium co-blended hole zinc oxide thin film material Download PDFInfo
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- CN100437908C CN100437908C CNB2004100890743A CN200410089074A CN100437908C CN 100437908 C CN100437908 C CN 100437908C CN B2004100890743 A CNB2004100890743 A CN B2004100890743A CN 200410089074 A CN200410089074 A CN 200410089074A CN 100437908 C CN100437908 C CN 100437908C
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- aluminium
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- thin film
- zinc oxide
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Abstract
The present invention relates to a nitrogen-aluminium codoping hollow cavity type zinc oxide film and a preparation process thereof. By adopting a supersonic spray pyrogenation method, the mixed solution of the organic or inorganic salt solution of Zn, the organic or inorganic salt solution of N, and the inorganic salt solution of Al is taken as a precursor. By adjusting the proportion of Zn< 2+ >, NH4< + > and Al< 3+ > which is 1 to (1 to 3) to (0.01 to 0.2) and controlling the substrate temperature from 600 to 900 DEG C. to realize the control over the electrical property of a p type ZnO film. The specific resistance of the p type ZnO film prepared by the present invention is 10<-1 > to 10 <-2 > omega cm, and the maximum mobility can reach 103cm< 2 >V<-1 >s<-1 >. Crystal grains of the film have uniform sizes and are arranged densely, and simultaneously, the film has the characteristics of strong (101) orientation of crystallization and ultraviolet light emission at normal temperature.
Description
Technical field
The present invention relates to be used for Zinc oxide-base light-emitting diode (LEDs), the preparation technology of a kind of nitrigen-aluminium co-blended hole zinc oxide thin film material of opto-electronic devices such as laser diode (LDs) and ultraviolet detector belongs to field of semiconductor materials.
Background technology
The huge market potential of zno-based photoelectric device has excited the research boom of ZnO material.The core of zno-based photoelectric device is a junction type ZnO material, and realizes that the key issue of p-n junction growth and development ZnO homogeneity and zno-based heterojunction photoelectric device is to solve the self compensation of ZnO and realizes that efficiently, controllably the p type mixes.And the high-quality p type ZnO film with low-resistance, high mobility is significant for the luminous efficiency that improves luminescent device and the photoelectric conversion efficiency of sensitive detection parts.But because there are many intrinsic alms giver's defectives in ZnO, as gap zinc Zn
iWith oxygen room V
o, its energy level lays respectively at 0.05eV and 0.3eV place at the bottom of the conduction band, gives birth to the auto-compensation of height to being subjected to main product.Therefore, be difficult to realize that the p type of ZnO changes.And, the acceptor level of ZnO generally very dark (except the N), the hole is difficult for thermal excitation and enters valence band, and the solid solubility of acceptor doping is also very low.Therefore the p type of low-resistance, high mobility mixes and is difficult to realize.The p type ZnO film performance of Japan big version river and laboratory development reaches higher level at present, and its resistivity is at 2-5 Ω cm, and carrier mobility is at 0.1-0.4cm simultaneously
2V
-1s
-1(people such as Xin-Li Guo, Optical Materials 19,229 (2002)).
The doping of p type ZnO film mainly contains five kinds of channels: 1. mix N 2.Ga, N and mix 3.In, N altogether and mix 4. altogether and mix As 5. and mix P.Active N source generally derives from N in first kind
2, N
2O or NH
3, but because N replaces the O atomic time, improved Madelung energy (Madelung Energy) thus caused the localization of N energy level, the N energy level is darker, the doping effect is not very desirable.Second and third kind will be used the higher Ga of price, In source, cost of manufacture height.The two kinds of acceptor levels in back are all deep, and the doping effect is undesirable, and As and P are poisonous.The codope of theoretical prediction N and Al will be better than other combinations of mixing can realize more effectively that the p type of ZnO changes (Wang, people such as L.G., Phys.Rev.Lett.90,256401 (2003) and Yamamoto, people such as T., Physica B, 302-303,155 (2001)).
At present, magnetron sputtering is adopted in the preparation of p type ZnO film more, pulsed laser deposition (PLD) technology, yet but suitable difficulty of the p type ZnO film that obtains low-resistance, high mobility.For example, the people such as Ohshima of Japanese Kumamoto university once utilized the N of ion gun emission
+Or N
2 +Ion sputtering Al mesh electrodes, thus the non-blended ZnO film of KrF excimer pulsed laser deposition is carried out N-Al codope people such as (, Thin Solid Films, 435,49 (2003)) T.Ohshima, but the result does not obtain p type ZnO film; By dc reactive magnetron sputtering technique ZnO is carried out the p type ZnO film that N-Al codope (people such as Ye Zhi town, Journal of Crystal Growth 265,127 (2004)) obtains, its resistivity is 10
2-10
4Ω cm, mobility is at 0.3-19cm
2V
-1s
-1Above-mentioned Japanese river and the laboratory p type ZnO film of the higher level of PLD method development, its resistivity is higher, and carrier mobility is also very low simultaneously, can't satisfy practical requirement.Reason is that these two kinds of methods all need high vacuum condition, so oxygen defect that has high concentration in the gained ZnO film, this makes the self compensation effect in the film significantly strengthen, adding that the concentration that N led is very low, is unusual difficulty so will make N that abundant holoe carrier is provided with the p type conduction that realizes ZnO.In addition, magnetron sputtering and PLD apparatus expensive, system film cost height is difficult to realize the large tracts of land deposition.And the ullrasonic spraying thermolysis process carries out under normal pressure, and this can make oxygen defect reduce in a large number.And the thermal chemical reaction that occurs in the mixed solution in the ullrasonic spraying thermal decomposition process is very favorable to the doping of ZnO film.Therefore the codope that adopts the ullrasonic spraying thermolysis process that ZnO film is carried out N and Al should be one of the effective ways of the p type ZnO film of preparation low-resistance, high mobility.This method equipment is simple, easy to operate, abundant raw material, and cost of manufacture is low.
Summary of the invention
The preparation technology who the purpose of this invention is to provide a kind of nitrogen aluminium codope cavity type (p type) zinc-oxide film.
The present invention is by the organic or inorganic salting liquid that contains Zn, contains the organic or inorganic salting liquid of N and contain the low-resistance of the thermal chemical reaction preparation of the mixed solution that the inorganic salt solution of Al forms, the p type ZnO film of high mobility, and its resistivity is 10
-1-10
-2Cm, mobility reaches as high as 103cm
2V
-1s
-1, with present international higher level (resistivity 2-5 Ω cm, carrier mobility 0.1-0.4cm
2V
-1s
-1) compare, resistivity has reduced by 2 orders of magnitude, and hall mobility has improved 2-3 the order of magnitude, and the homogeneous grain size of film, arranges fine and closely, and film has the crystallization property and the normal temperature ultra-violet light-emitting characteristic of strong (101) orientation simultaneously.
The preparation technology of nitrogen aluminium codope cavity type ZnO film of the present invention adopts the ullrasonic spraying thermal decomposition method, with putting into film forming room after the substrate surface cleaning and substrate being heated, with ultrasonic atomizer precursor solution is atomized then, again with air or high-purity N earlier
2, O
2, NH
3Or Ar makes gas aerosol imported film forming room, is being heated to the p type ZnO film that deposits low-resistance, high mobility on 600-900 ℃ the different materials substrate surface at last, and growth time is determined by desired thickness.
Contain Zn organic or inorganic salt in the above-mentioned precursor solution and can be zinc acetate or zinc nitrate or zinc chloride, contain N organic salt or inorganic salts and can be ammonium acetate or ammonium nitrate, the inorganic salts that contain Al can be aluminum nitrate or aluminium chloride.By regulating electric property that Zn, N, the atom doped ratio of Al and underlayer temperature can control the zno-based film particularly resistivity and mobility.
Implementation procedure of the present invention can be divided into following two parts:
1, the preparation of precursor solution:
Precursor solution is the aqueous solution, and main solute is chosen as:
The Zn source is zinc acetate (Zn (CH
3COO)
2) or zinc nitrate (Zn (NO
3)
2) or zinc chloride (ZnCl
2).
Zn
2+The concentration of solution is 0.1～1mol/L.
Doped chemical is selected N, Al, wherein:
The N source is ammonium acetate (CH
3COONH
4) or ammonium nitrate (NH
4NO
3).
NH
4 +Concentration is 1～5mol/L;
The Al source is aluminum nitrate (Al (NO
3)
3) or aluminium chloride (AlCl
3).
Al
3+Concentration is 0.1～1mol/L;
Precursor solution gram molecule proportioning is Zn
2+: NH
4 +: Al
3+=1: (1-3): (0.01-0.2).
2, the deposition of p type ZnO 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 p type ZnO film at the substrate surface that heats.The deposition rate of ZnO 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 600-900 ℃.
Gas is air or high-purity N
2, O
2, NH
3Or Ar.
The atomized soln wear rate is that every square centimeter of per minute is gone up consumption 0.06～0.6ml.
Nozzle and substrate distance are 3～10cm.
Advantage of the present invention has:
1) present device is simple, and is easy to operate, the Al abundant raw material, and cost of manufacture is low.
2) electrical property of film is controlled, and good stability can reach the purpose of controlling film resiativity and mobility by regulating Zn, N, the atom doped ratio of Al and underlayer temperature.
3) the p type ZnO film resistivity of the N-Al codope of gained of the present invention is 10
-1-10
-2Ω cm, mobility reaches as high as 103cm
2V
-1s
-1, with present international higher level (resistivity 2-5 Ω cm, carrier mobility 0.1-0.4cm
2V
-1s
-1) compare, resistivity has reduced by 2 orders of magnitude, hall mobility has improved 2-3 the order of magnitude, and have the film homogeneous grain size, arrange fine and close, have crystallization property and these good characteristics of normal temperature ultra-violet light-emitting characteristic of strong (101) orientation, therefore more can satisfy the application of zno-based photoelectric device.
Description of drawings
Fig. 1 is the improved ullrasonic spraying thermal decomposer schematic diagram that adopts according to the inventive method.
The parts that this device comprises have 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 ESEM (SEM) photo of nitrogen aluminium codoped p type ZnO film.This figure illustrates p type ZnO film homogeneous grain size, the arrangement densification of gained of the present invention.
Fig. 3 is X-ray diffraction (XRD) collection of illustrative plates of nitrogen aluminium codoped p type ZnO film.This figure illustrates that the p type ZnO film of gained of the present invention has the crystal structure of strong (101) orientation, and the thin film crystallization quality is higher.
Fig. 4 is light at room temperature photoluminescence (PL) collection of illustrative plates of nitrogen aluminium codoped p type ZnO film.This figure shows that the p type ZnO film of gained of the present invention has extremely strong nearly band edge ultraviolet emission peak (378nm), and the emission peak relevant (510nm) with fault of construction almost survey less than, prove that film has high optical quality, and film in defect density very low.
Embodiment
Below with reference to Fig. 1, 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 by embodiment.
Substrate adopts (100) face monocrystalline silicon piece.The precursor solution proportioning is: 1mol/L Zn (CH
3COO)
25mL, 5mol/L CH
3COONH
43mL, 0.5mol/L Al (NO
3)
30.5mL.Solvent all adopts deionized water.The precursor solution for preparing is poured in the ultrasonic atomization cup.Monocrystalline (100) silicon chip, is fixed on the stone or metal plate for standing a stove on as a precaution against fire after 3 minutes at once with the hydrofluoric acid etch, stone or metal plate for standing a stove on as a precaution against fire is heated to 700 ℃, treat that substrate reaches design temperature after, start ultrasonic ultrasonic delay line memory, with high-purity N
2(99.999%) make gas, film forming room keeps air atmosphere simultaneously, and the gas after the atomizing enters film forming room through the gas-liquid separation pipe, and keeping nozzle is about 5 centimetres to substrate distance, stops to spray in about 10 minutes.The precursor solution wear rate is that every square centimeter of per minute is gone up consumption 0.2ml.Reduce to room temperature 700 ℃ of insulations after 5 minutes.
The ZnO 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 1.7 * 10
-2Ω cm.Carrier mobility 73.6cm
2V
-1s
-1Carrier concentration 5.09 * 10
18Cm
-3The conduction type of the ZnO film that Seebeck effect test result conclusive evidence is grown is the p type.
The precursor solution proportioning is: 1mol/L Zn (CH
3COO)
25mL, 5mol/L CH
3COONH
42mL, 0.5mol/L AlCl
30.5mL.Underlayer temperature is 650 ℃.Spray time 6 minutes.Thin film deposition finishes, and reduces to room temperature 650 ℃ of insulations after 5 minutes.Other condition is with example 1.The ZnO film of growth is through the Hall effect test shows, and conduction type is p type, i.e. hole conduction.Resistivity 1.6 * 10
-2Ω cm, carrier mobility 103cm
2V
-1s
-1, carrier concentration 3.81 * 10
18Cm
-3
Claims (7)
1, a kind of preparation technology of nitrigen-aluminium co-blended hole zinc oxide thin film material comprises the steps:
(1) precursor solution in preparation zinc source, nitrogenous source and aluminium source, the gram molecule proportioning is Zn in the solution
2+: NH
4 +: Al
3+=1: (1-3): (0.01-0.2);
(2) precursor solution atomizes through ultrasonic ultrasonic delay line memory, again with air or high-purity N
2, O
2, NH
3Or Ar do gas with the precursor solution of atomizing through gas-liquid separation pipe input film forming room, the monocrystalline silicon piece, quartz glass plate or the sapphire sheet substrate surface that are ejected in heating through nozzle are deposited as the cavity type ZnO film, underlayer temperature is controlled at 600-900 ℃.
2, by the preparation technology of the described a kind of nitrigen-aluminium co-blended hole zinc oxide thin film material of claim 1, it is characterized in that described zinc source is the organic or inorganic salting liquid of Zn, nitrogenous source is the organic or inorganic salting liquid of N, and the aluminium source is the inorganic salt solution of Al.
3, by the preparation technology of the described a kind of nitrigen-aluminium co-blended hole zinc oxide thin film material of claim 1, it is characterized in that described zinc source is zinc acetate (Zn (CH
3COO)
2) or zinc nitrate (Zn (NO
3)
2) or zinc chloride (ZnCl
2), Zn
2+The concentration of solution is 0.1～1mol/L.
4, by the preparation technology of the described a kind of nitrigen-aluminium co-blended hole zinc oxide thin film material of claim 1, it is characterized in that described nitrogenous source is ammonium acetate (CH
3COONH
4) or ammonium nitrate (NH
4NO
3), NH
4 +Concentration is 1～5mol/L.
5, by the preparation technology of the described a kind of nitrigen-aluminium co-blended hole zinc oxide thin film material of claim 1, it is characterized in that described aluminium source is aluminum nitrate (Al (NO
3)
3) or aluminium chloride (AlCl
3), Al
3+Concentration is 0.1～1mol/L.
6,, it is characterized in that the precursor solution wear rate that atomizes is that every square centimeter of per minute is gone up consumption 0.06～0.6ml by the preparation technology of claim 1 or 2 or 3 or 4 described a kind of nitrigen-aluminium co-blended hole zinc oxide thin film materials.
7, by the preparation technology of claim 1 or 2 or 3 or 4 described a kind of nitrigen-aluminium co-blended hole zinc oxide thin film materials, it is characterized in that described nozzle and substrate distance are 3～10cm.
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|---|---|---|---|
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| CN100437908C true CN100437908C (en) | 2008-11-26 |
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|---|---|---|---|---|
| CN100404142C (en) * | 2006-07-24 | 2008-07-23 | 南开大学 | Thermal decomposing nozzle for ultrasonic spraying |
| CN113265115B (en) * | 2021-04-26 | 2022-04-01 | 山东大学 | Nitrogen-aluminum co-doped carbon dot film laser protection material and preparation method and application thereof |
| CN113285049B (en) * | 2021-05-27 | 2022-05-06 | 电子科技大学 | Method for preparing tungsten trioxide OLED external light extraction layer with high light extraction efficiency by ultrasonic spraying |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6410162B1 (en) * | 1998-08-03 | 2002-06-25 | The Curators Of The University Of Missouri | Zinc oxide films containing P-type dopant and process for preparing same |
| CN1527361A (en) * | 2003-09-19 | 2004-09-08 | 中国科学院上海硅酸盐研究所 | N and In codoping process in preparing hole type zinc oxide film |
| CN1547264A (en) * | 2003-12-05 | 2004-11-17 | 中国科学院上海硅酸盐研究所 | Zinc oxide homogeneous p-n junction material and method for making same |
-
2004
- 2004-12-03 CN CNB2004100890743A patent/CN100437908C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6410162B1 (en) * | 1998-08-03 | 2002-06-25 | The Curators Of The University Of Missouri | Zinc oxide films containing P-type dopant and process for preparing same |
| CN1527361A (en) * | 2003-09-19 | 2004-09-08 | 中国科学院上海硅酸盐研究所 | N and In codoping process in preparing hole type zinc oxide film |
| CN1547264A (en) * | 2003-12-05 | 2004-11-17 | 中国科学院上海硅酸盐研究所 | Zinc oxide homogeneous p-n junction material and method for making same |
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