CN101280414A - ZnO: Bi photoemissive thin film and preparation thereof - Google Patents

ZnO: Bi photoemissive thin film and preparation thereof Download PDF

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CN101280414A
CN101280414A CNA2008100734090A CN200810073409A CN101280414A CN 101280414 A CN101280414 A CN 101280414A CN A2008100734090 A CNA2008100734090 A CN A2008100734090A CN 200810073409 A CN200810073409 A CN 200810073409A CN 101280414 A CN101280414 A CN 101280414A
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CN100595319C (en
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江民红
刘心宇
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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Abstract

The invention discloses a ZnO:Bi photoelectric thin film and the preparation method thereof. Analytically pure Bi2O3 powder is taken as doping material, and the nanometer zinc oxide with 99.95 percent of fineness is taken as main body material, the incorporation amount of the Bi2O3 powder is 1 to 5 percent of total weight, mixture is mixed by ball milling for 360 to 720 minutes, and is extruded for 3 to 15 minutes under the pressure intensity of 30 to 60 MPa for molding, the heat preservation and the sintering are performed for 60 to 360 minutes under normal pressure at 1200 to 1400 DEG C in the air, and ZnO:Bi ceramic target material is prepared. The film is prepared by adopting a radio frequency magnetic controlled sputtering method under the condition that the degree of vacuum is 8.0 multiplied by 10 <-5> Pa and the gas pressure intensity after the pure argon is filled is 1 to 3 Pa, and then the film is prepared by the annealing heat treatment under the vacuum circumstance with the vacuum degree less than or equal to 0.1 Pa, the expression formula is ZnO:Bi, and the weight ratios of the use amount of all raw materials are ZnO 95-99 percent and Bi2O3 1-5 percent. The photoelectric thin film has good photoelectric performance, the specific resistance reaches 9.0 multiplied by 10<-4> ohms*cm, the transmissibility of visible light reaches above 85 percent, the transmissibility of an ultraviolet band with the wavelength lower than 370 nm is expressed as the cut off state, the ZnO:Bi photoelectric thin film has good ultraviolet stealth effect, and the purity of the raw materials adopted is low, the process is simple, and the cost is low.

Description

ZnO:Bi optoelectronic film and preparation method thereof
Technical field:
The present invention relates to photoelectron material, specifically is ZnO:Bi optoelectronic film and preparation method thereof.
Background technology:
Zno-based semiconductor light conductive film as a kind of to the visible transparency height, conduct electricity very well, the film material with function that also has characteristics such as piezoelectricity and air-sensitive simultaneously, because of its have abundant raw material, inexpensive nontoxic, plasma neutral can stablize and can gap length etc. series of advantages, have and replace expensive rare, that the partial properties index is on the low side, deleterious, the indium oxide film (In that mixes tin 2O 3: Sn, be called for short ITO) etc. the very big potentiality of optoelectronic film, can be widely used in solar cell, indicating meter, laser apparatus, electromagnetic shielding, fields such as antistatic coating, piezoelectric device and air-sensitive assembly.
In recent years, in order to improve the over-all properties of ZnO optoelectronic film, often ZnO is carried out different element doping modifications.At present, mix elements such as Al, Ga, rare earth or the polynary ZnO film of mixing altogether and be used various processing methodes and prepared, as:
[1]Kim?K.H，Park?K.C，Ma?D.Y.Structural，eletrical?and?optical?properties?ofaluminumdoped?zinc?oxide.films?prepared?rf-magnetron?sputtering[J].Appl.Phys，1997，81(12)：7764-772；
[2]K.Saito，Y.Hiratsuka，A.Omata，H.Makino，S.Kishimoto，T.Yamamoto，N.Horiuchi?and?H.Hirayama.atomic?layer?deposition?and?characterization?of?Ga-dopedZnO?thin?films.superlattices?and?Microstructures，2007，42(1-6)：172-175；
[3]Tadatsugu?Minami，Takashi?Yamamoto，Toshihiro?Miyata.Highlytransparent?and?conductive?rare?earth-doped?ZnO?thin?films?prepared?by?magnetronsputtering[J].Thin?Solid?Films，366(2000)：63-68；
[4]Tadatsgumu?Minami，Shingo?Suzuki，Toshihiro?Miyata.Transparentconducting?impurity-co-doped?ZnO:Al?thin?fims?prepared?by?magnetron?sputtering[J].Thin?Solid?Films，2001，398-399：53-58；
[5] Chinese patent application number is 200610043274.4 to disclose a kind of ZnO:Mo transparent conductive film and preparation method, and this invention ZnO is base-material and M 0O 3Powder is by weight thorough mixing, and after the compression moulding, high temperature waters and forms ZnO:M in air oTarget as for carrying in the glass basis sheet of cleaning, is put into magnetic control sputtering device to target, argon gas sputter and make ZnO:M oTransparent conductive film, but the resistivity of this optoelectronic film is still bigger, and low to the cutoff rate of UV-light, Mo belongs to rare precious metal, the cost height simultaneously.
So far, also make the report of ZnO:Bi transparent conductive film less than doping Bi element in ZnO.Simultaneously, among the ZnO thin film doped preparation method of above-mentioned all non-Bi, the purity of its doped raw material and matrix material all requires high, all reaches 99.99% (4N).
Summary of the invention
The purpose of this invention is to provide a kind of novel visible light transmissivity height, good conductivity, (＜370nm) shielding effect, material purity is low, simple, lower-cost ZnO:Bi optoelectronic film of technology and preparation method thereof to have ultraviolet.
A kind of ZnO:Bi optoelectronic film, it is with bismuth oxide (Bi 2O 3) as doped raw material, zinc oxide (ZnO) is formed Bi for material of main part 2O 3Incorporation be the 1-5% of gross weight, through ball milling mix, compression moulding, high temperature sintering is made ceramic target, target prepares film through rf magnetron sputtering again, again the optoelectronic film that makes is carried out vacuum heat treatment and obtain, expression formula is ZnO:Bi, and each component raw material consumption weight percent is:
ZnO 95-99％；
Bi 2O 3 1-5％。
At above-mentioned ZnO:Bi optoelectronic film, the invention provides following corresponding preparation method:
A kind of magnetron sputtering method prepares the method for ZnO:Bi optoelectronic film, comprises the steps:
(1) with purity is nano-ZnO and the analytical pure Bi of 99.95wt% 2O 3Powder is prepared by weight percentage, through ball milling thorough mixing 360-720min, after pressurize 3-15 minute compression moulding under the pressure of 30-60MPa, place high temperature sintering furnace, 1200-1400 ℃ of following normal pressure, heat preservation sintering 60-360 minute in air are prepared into the ZnO:Bi ceramic target;
(2) with the target and the slide glass of step (1) through cleaning, the magnetic control sputtering device of packing into, sputter prepares the ZnO:Bi optoelectronic film, and sputter base vacuum degree is better than 8.0 * 10 -5Pa, sputter gas are argon gas, and air pressure is 1-3.0Pa, and sputtering power is 30-110W, and sputtering time is 15-60 minute, and thickness is 100-500nm;
(3) the ZnO:Bi optoelectronic film with step (2) was vacuum-sealed in silica tube or the Glass tubing, at 300-550 ℃ of following insulation annealing 120-300 minute.
When preparing target in the above-mentioned steps (1), what preferentially select is: Bi 2O 3The ratio of the shared gross weight of powder is 3%, and the ball mill mixing time is 720 minutes, and forming pressure is 60MPa, and 5 minutes dwell times, sintering temperature and sintering time are respectively 1350 ℃ and 240 minutes;
When preparing film in the above-mentioned steps (2), what preferentially select is: Ar Pressure is 1.6Pa, and sputtering power is 75W, and sputtering time is 60 minutes;
The magnetron sputtering method that adopts in the above-mentioned steps (2) is a radio-frequency magnetron sputter method; The slide glass that adopts, successively at deionized water, acetone and dehydrated alcohol through ultrasonic cleaning, and in dehydrated alcohol, preserve standby;
When in the above-mentioned steps (3) the ZnO:Bi optoelectronic film being heat-treated, preferential select is: film is vacuum-sealed in the silica tube anneals, holding temperature is 400 ℃, and soaking time is 180 minutes;
In the above-mentioned steps (3), vacuum tightness is 0.1Pa in the silica tube.
The present invention will realize ZnO thin film doped semiconductor according to the solid solution theory, requires dopant ion and substituted ionic radius to be close, and can realize alms giver or acceptor doping, and can not form new compound.Doped element Bi of the present invention 3+Radius be 9.6 * 10 -11M, Zn 2+Radius be 7.4 * 10 -11M, both radius ratios are more approaching, and the Bi atom is tervalent, and the Zn atom is a divalence, the Bi atom trends towards with Bi 3+The mode generation solid solution of+3e, Bi 3+Ion occupies Zn in the lattice 2+The position, the combination of two participations with oxygen arranged in three valence electrons of Bi, the 3rd electronics can not enter now saturated key, it is separated from impurity atoms and forms a monovalence center of positive charge Bi ZnWith a unnecessary valence electron, the energy level of this electronics is arranged in energy gap and is lower than the conduction band bottom slightly, and at normal temperatures, this electronics is with regard to obtaining enough energy and transitting on the conduction band from donor level and become unbound electron, orientation movement under the extra electric field effect and conducting electricity.Therefore the result who mixes Bi has increased clean electronics, and the zinc oxide films membrane conductivity is increased.
ZnO:Bi optoelectronic film of the present invention is known through X-ray diffraction analysis, has the hexagonal wurtzite structure of strong (002) preferred orientation growth; Through carrying out photoelectric properties tests, this film has good electrical conductivity, has good transmittance in the visible region, simultaneously ultraviolet band (＜370nm) transmitance is zero, shows as off condition, therefore has very strong ultraviolet stealth effect at this wave band.
The invention has the advantages that: raw materials used purity is low, ZnO that is adopted and Bi 2O 3Purity only require to be respectively 99.95% and analytical pure, UV-light (＜370nm) transmitance is zero, presents shielding effect, the visible light transmissivity height, resistivity is little, conducts electricity very well, technology is simple, cost is low.
Description of drawings:
Fig. 1 composes for the XRD figure of the ZnO:Bi film that sputter in the embodiment of the invention 1 makes;
Seeing through-absorption spectrum of the ZnO:Bi film that Fig. 2 makes for sputter in the embodiment of the invention 1.
Embodiment
The several embodiment of various details, but content of the present invention is not limited to this fully.
Embodiment 1:
A kind of preparation method of ZnO:Bi optoelectronic film comprises the steps:
(1) with purity is nano-ZnO and the analytical pure Bi of 99.95wt% 2O 3Powder is by weight: ball milling mixed 720 minutes in 97: 3, after compression moulding under the pressure of 60Mpa, placed high temperature sintering furnace, and 1350 ℃ of following normal pressures, heat preservation sintering are 240 minutes in air, are prepared into the ZnO:Bi ceramic target.
(2) selecting common slide glass for use is substrate, substrate is successively carried out at deionized water, acetone and dehydrated alcohol through ultrasonic cleaning, and with the target and the slide glass of step (1) through cleaning, the rf magnetron sputtering instrument of packing into, sputter base vacuum degree is 8.0 * 10 -5Pa, sputter gas are argon gas, and air pressure is 1.6Pa, and sputtering power is 75W, and sputtering time is 60 minutes, and sputter prepares the ZnO:Bi optoelectronic film, and thickness is 200nm;
(3) the ZnO:Bi optoelectronic film with step (2) was vacuum-sealed in silica tube or the Glass tubing, 400 ℃ of following insulation annealings 180 minutes.The resistivity of annealing rear film is 9.0 * 10 -4Ω cm.
The XRD figure of prepared ZnO:Bi film is composed as shown in Figure 1, and as seen from the figure, this film has the hexagonal wurtzite structure of (002) preferred orientation growth strongly, and the C axle is perpendicular to substrate.
The seeing through of prepared ZnO:Bi film-absorption spectrum as shown in Figure 2, as seen from the figure, the visible light transmissivity of this film is more than 85%, film is zero at wavelength less than the ultraviolet band transmitance of 370nm simultaneously.
Embodiment 2:
The processing step of this embodiment is with embodiment 1, but different be that sputtering time is 30 minutes in the step (2), film thickness is 100nm, film resiativity is 1.5 * 10 -2Ω cm, transmitance is more than 85%, in the certain light transmission of ultraviolet band performance.
Embodiment 3:
The processing step of this embodiment is with embodiment 1, but different be in the step (2), Sputtering Ar, air pressure is 3Pa, film thickness is 200nm, film resiativity is 1.5 * 10 -3Ω cm, visible light transmissivity be more than 85%, and film is zero at wavelength less than the ultraviolet band transmitance of 370nm simultaneously.
Embodiment 4:
The processing step of this embodiment is with embodiment 1, but different is in the step (3), 400 ℃ of following insulation annealings are 180 minutes in air, film thickness is 200nm, film resiativity is up to 40 Ω cm, visible light transmissivity is more than 80%, and film is zero at wavelength less than the ultraviolet band transmitance of 370nm simultaneously.
Embodiment 5:
The processing step of this embodiment is with embodiment 1, but different be not have step (3), film thickness is 200nm, film resiativity is much larger than 40 Ω cm, visible light transmissivity is more than 80%.
Embodiment 6:
The processing step of this embodiment is with embodiment 1, but different be in the step (1), nano-ZnO and Bi 2O 3The powder weight ratio is 95: 5, and film thickness is 300nm, and film resiativity is 1.8 * 10 -3Ω cm, transmitance is more than 80%.

Claims (5)

1, a kind of ZnO:Bi optoelectronic film, it is characterized in that: it is with Bi 2O 3As doped raw material, zinc oxide is that material of main part is formed Bi 2O 3Incorporation be the 1-5% of gross weight, after batching, ball milling mixing, compression moulding, high-temperature firing become ceramic target, be 8.0 * 10 at the base vacuum degree -5Pa, the gas pressure intensity that fills behind the straight argon are under the condition of 1-3Pa, and through rf magnetron sputtering system film, annealing thermal treatment is made in the vacuum environment of vacuum tightness＜0.1Pa again, and expression formula is ZnO:Bi, and each component raw material consumption weight ratio is ZnO 95-99%, Bi 2O 31-5%.
2, a kind of preparation method of ZnO:Bi optoelectronic film comprises that ball milling mixes, compression moulding, and high temperature sintering potting porcelain target, target is characterized in that again through magnetron sputtering:
(1) be to mix analytical pure Bi in 99.95% nano-ZnO in purity 2O 3, ball milling mixing 360-720 minute, compacting moulding in 3-15 minute under the pressure of 30-60MPa, 1200-1400 ℃ of following normal pressure, heat preservation sintering 60-360 minute in air are prepared into the ZnO:Bi target;
(2) the base vacuum degree of rf magnetron sputtering is 8.0 * 10 -5Pa, the Ar Pressure during sputter is 1-3Pa, and sputtering power is 30-110W, and sputtering time is 15-120 minute;
(3) used slide glass successively at deionized water, acetone and dehydrated alcohol through ultrasonic cleaning;
(4) carry out vacuum heat treatment: the ZnO:Bi optoelectronic film of gained was sealed in the silica tube or Glass tubing of vacuum tightness＜0.1Pa behind the magnetron sputtering, at 300-550 ℃ of following insulation annealing 120-300 minute.
3, preparation method as claimed in claim 2 is characterized in that: in the step (1) preferably: the ball mill mixing time is 720 minutes, and forming pressure is 60MPa, and 5 minutes dwell times, sintering temperature and sintering time are respectively 1350 ℃ and 240 minutes.
4, preparation method as claimed in claim 2 is characterized in that: in the step (2) preferably: Ar Pressure is 1.6Pa, and sputtering power is 75W, and sputtering time is 60 minutes.
5, preparation method as claimed in claim 2 is characterized in that: in the step (4) preferably: holding temperature is 400 ℃, annealing soaking time be 180 minutes.
CN200810073409A 2008-01-07 2008-01-07 ZnO:Bi photoemissive thin film and preparation thereof Expired - Fee Related CN100595319C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107102383A (en) * 2016-02-22 2017-08-29 株式会社腾龙 Infrared transmitting film, optical film, antireflection film, optical component, optical system and camera device
CN109078633A (en) * 2018-08-24 2018-12-25 西南交通大学 A kind of W doping Bi2O3The preparation method of nanostructure
CN111957579A (en) * 2019-05-20 2020-11-20 米亚索乐装备集成（福建）有限公司 Powder screening method and system
CN115724466A (en) * 2022-10-28 2023-03-03 佛山市明事达智能材料有限公司 Zinc oxide composite material and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5396494A (en) * 1977-02-02 1978-08-23 Murata Manufacturing Co Piezooelectric crystal film of zinc oxide
KR100470155B1 (en) * 2003-03-07 2005-02-04 광주과학기술원 Manufacturing method of zinc oxide semiconductor
CN1333103C (en) * 2003-10-10 2007-08-22 桂林电子工业学院 High-density ITO targe material and preparing method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107102383A (en) * 2016-02-22 2017-08-29 株式会社腾龙 Infrared transmitting film, optical film, antireflection film, optical component, optical system and camera device
CN107102383B (en) * 2016-02-22 2020-04-10 株式会社腾龙 Infrared-transmitting film, optical film, antireflection film, optical member, optical system, and imaging device
CN109078633A (en) * 2018-08-24 2018-12-25 西南交通大学 A kind of W doping Bi2O3The preparation method of nanostructure
CN111957579A (en) * 2019-05-20 2020-11-20 米亚索乐装备集成（福建）有限公司 Powder screening method and system
CN115724466A (en) * 2022-10-28 2023-03-03 佛山市明事达智能材料有限公司 Zinc oxide composite material and preparation method and application thereof
CN115724466B (en) * 2022-10-28 2023-07-18 佛山市明事达智能材料有限公司 Zinc oxide composite material and preparation method and application thereof

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