CN105420677B - The preparation method of the p-type tin dioxide thin film of nearly band edge ultra-violet light-emitting can be achieved - Google Patents

The preparation method of the p-type tin dioxide thin film of nearly band edge ultra-violet light-emitting can be achieved Download PDF

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CN105420677B
CN105420677B CN201510880868.XA CN201510880868A CN105420677B CN 105420677 B CN105420677 B CN 105420677B CN 201510880868 A CN201510880868 A CN 201510880868A CN 105420677 B CN105420677 B CN 105420677B
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sno
film
emitting
violet light
ultra
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CN105420677A (en
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李永峰
贾金环
姚斌
丁战辉
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Jilin University
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Jilin University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5866—Treatment with sulfur, selenium or tellurium

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Led Devices (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention relates to the preparation method for the p-type tin dioxide thin film that nearly band edge ultra-violet light-emitting can be achieved.It is characterized in that with metallic tin (Sn), metallic antimony (Sb), nitrogen (N2), oxygen (O2), sulphur powder (S) be raw material, using magnetron sputtering technique and sulphur atmosphere heat treatment technology, prepare the p-type SnO with high hole concentration and nearly band edge ultra-violet light-emitting2Film, the concentration range of its holoe carrier is 1018cm‑3To 1019cm‑3, room temperature ultra-violet light-emitting wave-length coverage is 380nm to 390nm.This method uses alms giver's recipient element codoping technology and sulphur atmosphere heat treatment technology, improves acceptor in SnO2In solid solubility, and break electronics in SnO2Conduction band bottom and the abstinence rule of top of valence band transition, realize nearly band edge ultra-violet light-emitting, available for the p-type electric-conducting layer prepared in broad-band gap oxide photoelectric device.

Description

The preparation method of the p-type tin dioxide thin film of nearly band edge ultra-violet light-emitting can be achieved
Technical field
The present invention relates to a kind of p-type SnO that nearly band edge ultra-violet light-emitting can be achieved2The preparation method of film, this method is with gold Belong to tin (Sn), metallic antimony (Sb), nitrogen (N2), oxygen (O2), argon gas (Ar) sulphur powder (S) be raw material, belong to optoelectronic thin-film material Field.
Background technology
SnO2A kind of direct broad-band gap oxide semiconductor, its basic band gap and optical band gap be respectively 3.3eV and 3.6eV, due to it have higher visible light transmissivity and stronger electronic conduction ability, be applied to transparent conductive film, The fields such as solar cell, photocatalysis.Although SnO2For direct band gap material, but due to the limitation of its crystal structure symmetry, electricity Transition of the son between conduction band bottom and top of valence band is abstinence, i.e. SnO2The nearly band edge corresponding with basic band gap can not possibly be produced Ultra-violet light-emitting, this just greatly limit SnO2Application of the material in ultra-violet light-emitting field.In addition, SnO2Easily formed in crystal all Such as Lacking oxygen donor-type defect, SnO2Strongly n-type conductance is usually expressed as, due to compensating effect, the SnO of p-type conductance2It is more difficult to obtain , seriously constrain SnO2Application of the material in ultraviolet light photo field.Therefore, the p of achievable nearly band edge ultra-violet light-emitting is developed Type SnO2The preparation method tool of film is of great significance.
The content of the invention
It is an object of the invention to utilize donor-acceptor co-doping method, break SnO2Middle electronics is in conduction band bottom and valence band The abstinence rule of transition is pushed up, and overcomes acceptor in SnO2The low shortcoming of middle solid solubility, then be heat-treated by the later stage under sulphur atmosphere, To reduce acceptor's ionization energy, to obtain the p-type SnO of high hole concentration2Film.After the present invention will be using Sb, N codope and combination Phase sulphur atmosphere heat treatment technology, to prepare the p-type SnO of achievable nearly band edge ultra-violet light-emitting2Film.
The object of the present invention is achieved like this：Using metallic tin and metallic antimony as target, with the mixed of argon gas, oxygen and nitrogen Conjunction gas be sputter gas, using sapphire crystal as substrate, underlayer temperature be 300 DEG C under conditions of, cosputtering metallic tin and Metallic antimony target 60min, prepares Sb, N codope SnO2Film.By the SnO of preparation2Film is heat-treated under sulphur atmosphere, is obtained Sb, N codope SnO after heat treatment2Film.Photoluminescence measurement shows that the film has nearly band edge ultra-violet light-emitting The spectral characteristic being dominant.The test of room temperature Hall effect shows that the conduction type of the film is p-type, and carrier concentration is 1018cm-3 To 1019cm-3Between.
P-type SnO is prepared by the present invention2The advantage of film is：
(1) Sb alms giver and N recipient element codopes are used, N acceptors are improved in SnO2Middle solid solubility, and realize nearly band Side ultra-violet light-emitting.
(2) by the heat treatment in sulphur atmosphere, p-type SnO is improved2The hole of film, and enhance Ultra-violet light-emitting.
Brief description of the drawings
(1) Fig. 1 is process chart
(2) Fig. 2 is the SnO of Sb, N codope prepared2The X-ray diffraction pattern of film
(3) Fig. 3 is the SnO of Sb, N codope prepared2The Photoluminescence of film
Embodiment
Embodiment
Metallic tin and metallic antimony that diameter and thickness are respectively 60mm and 3mm are installed to two targets of magnetron sputtering apparatus On position, c surface sapphires are put on the heating furnace of growth room (specimen holder), system air pressure is evacuated to 1 × 10 with vavuum pump-4Pa, Sapphire Substrate is heated to 300 DEG C, it is 1 to be passed through volume ratio:2:The mixed gas of 1 argon gas, oxygen and nitrogen, gas flow is Air pressure in 40SCCM, regulation growth room is 1Pa, and the sputtering power of tin target and antimony target is adjusted into 70W and 25W respectively, two are removed Individual target position baffle plate, cosputtering 60min obtains the SnO of not thermally treated Sb, N codope2Film.This film is placed in annealing In stove, and 30mg sulphur powders uniformly are put into around film, annealing furnace air pressure are evacuated to below 0.1Pa with vavuum pump, argon gas is passed through, Gas flow is 40SCCM, is warming up to 5 DEG C/s speed after 600 DEG C, keeps 15min, then naturally cools to room temperature, is obtained Sb, N codope SnO after heat treatment2Film.Fig. 2 is the SnO of Sb, N codope before and after heat treatment2The X-ray diffraction pattern of film, Its diffracting spectrum shows that the film prepared is (200) preferred orientation, and second phase related to impurity is not found, illustrates to obtain Sb, N The SnO of codope2For single phase structure.Fig. 3 is the SnO of Sb, N codope before and after heat treatment2The room temperature photoluminescence of film Spectrum, with undoped with SnO2Film is compared, the SnO of Sb, N codope before and after heat treatment2Film occurs in that ultra-violet light-emitting, especially After it is heat treatment, the ultra-violet light-emitting at 380nm is remarkably reinforced, and strengthens about 4 times.Table 1 is co-doped with for Sb, N before and after heat treatment Miscellaneous SnO2The room temperature electrical properties of film, the SnO of Sb, N codope before and after heat treatment2Film is p-type conductance, and at heat Hole after reason reaches 1018cm-3Magnitude.As a comparison, a pure SnO undoped with Sb, N2The phase of film Answer characterization result be also respectively displayed on Fig. 2,3 and table 1 in.
The room temperature electrical properties of the SnO2 films of Sb, N codope prepared by table 1

Claims (4)

1. the preparation method of the p-type tin dioxide thin film of nearly band edge ultra-violet light-emitting can be realized, it is characterised in that with metallic tin (Sn), Metallic antimony (Sb) is target, argon gas (Ar), oxygen (O2) and nitrogen (N2) mixed gas as sputter gas, splashed using magnetic control Technology is penetrated on a sapphire substrate while splash-proofing sputtering metal target, prepares the SnO of Sb, N codope2Film, the film of acquisition is existed After being heat-treated under sulphur atmosphere, the p-type SnO of Sb, N codope is obtained2Film.
2. according to the preparation method described in claim 1, it is characterised in that be heat-treated the SnO of Sb, N codope under sulphur atmosphere2Film When, heating rate is controlled in 5 DEG C/s to 10 DEG C/s, is warming up to after 600 DEG C, keeps 15min.
3. according to the preparation method described in claim 1, it is characterised in that the p-type SnO of acquisition2The hole of film 1018cm-3To 1019cm-3Between, resistivity is between 6 Ω .cm to 16 Ω .cm.
4. according to the preparation method described in claim 1, it is characterised in that the p-type SnO of acquisition2Film room temperature photoluminescence spectrum Ultra-violet light-emitting peak is between 380nm to 390nm, and the halfwidth degree of glow peak is between 13nm to 28nm.
CN201510880868.XA 2015-12-03 2015-12-03 The preparation method of the p-type tin dioxide thin film of nearly band edge ultra-violet light-emitting can be achieved Expired - Fee Related CN105420677B (en)

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