CN109518149A - Along the preparation method of the antimony selenide optoelectronic film of<002>direction preferential growth - Google Patents

Along the preparation method of the antimony selenide optoelectronic film of<002>direction preferential growth Download PDF

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CN109518149A
CN109518149A CN201910012399.8A CN201910012399A CN109518149A CN 109518149 A CN109518149 A CN 109518149A CN 201910012399 A CN201910012399 A CN 201910012399A CN 109518149 A CN109518149 A CN 109518149A
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film
antimony
sputtering
preferential growth
preparation
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CN109518149B (en
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陈世建
周虹鹏
冯孟磊
张丁可
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Chongqing 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic 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
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5866—Treatment with sulfur, selenium or tellurium

Abstract

The present invention provides a kind of preparation method of the antimony selenide optoelectronic film of edge<002>direction preferential growth, include the following steps: that (a) prepares Mo/SLG conductive film: (b) prepares the metallic antimony film Sb/Mo/SLG along<003>orientation on the basis of step (a)；(c) the metallic antimony film Sb/Mo/SLG of above-mentioned preparation is finally put into vacuum degree is 1 × 10‑4‑9×10‑4It is that selenium is added in 1.5-3 in the quartz ampoule of Pa and by Se/Sb the mass ratio of the material, so that antimony film is completely converted into Sb2Se3；Then quartz ampoule is transferred in Muffle furnace and carries out calcination process, obtains the antimony selenide optoelectronic film along<002>direction preferential growth.There is carrier of the selenizing Sb film prepared using method of the invention along<002>direction highest mobility to have a wide range of applications potentiality in optical electro-chemistry field so as to which optical electro-chemistry hydrogen generation efficiency is greatly improved.

Description

Along the preparation method of the antimony selenide optoelectronic film of 002 direction > preferential growth of <
Technical field
The invention belongs to field of photoelectric material preparation, and in particular to a kind of antimony selenide light of edge<002>direction preferential growth The preparation method of conductive film.
Background technique
Antimony selenide (Sb2Se3) it is a kind of novel optoelectronic materials, its forbidden bandwidth is 1.1-1.2eV, it is similar with silicon (Si), But compared with silicon, antimony selenide has very high absorption coefficient (antimony selenide 105cm-1, silicon is~103cm-1), therefore be suitable for For film light absorbing material.Orthorhombic phase selenizing sb structure exists simultaneously covalent bond and Van der Waals key, is a kind of typical two-dimensional layer Shape material.In selenizing sb structure, Sb4Se6Basic structural unit (hereinafter referred to as ribbon unit) is along c- axis with covalently bound Form infinitely extends, and is by Sb along a- axis and b- axis direction4Se6It is connected with each other with weaker Van der Waals key.Therefore, Antimony selenide is a kind of crystal structure of height anisotropic, thus the transport efficiency of electric charge carrier is also anisotropic.So And there is highest mobility along the carrier of the direction ribbon (c- axis, i.e.<002>direction), along the defeated of other two axis Capacity power is relatively weak, and the selenizing Sb film along the direction ribbon (i.e.<002>direction) can greatly promote optical electro-chemistry H2-producing capacity.
Therefore, the antimony selenide optoelectronic film for preparing a kind of edge<002>direction preferential growth has a very important significance.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of edge<002>directions preferentially The preparation method of the antimony selenide optoelectronic film of growth, this method is by utilizing Sb2Se3Anisotropic growth rate itself, and Sb (003) facilitate to further suppress Sb2Se3Film other crystal orientation growth rate, while the selenium saturated vapor of balance depress To Sb2Se3Film is sintered, the common inducing action of this three prepares<002>with highest carrier mobility The selenizing Sb film of direction preferentially, so as to greatly improve optical electro-chemistry hydrogen generation efficiency.
To achieve the above object, the invention provides the following technical scheme: a kind of antimony selenide of edge<002>direction preferential growth The preparation method of optoelectronic film, includes the following steps:
(a) Mo/SLG conductive film is prepared:
(a1) successively it is cleaned by ultrasonic soda lime glass substrates with acetone, alcohol and deionized water, and is immersed in alcohol, uses When dried up with hair dryer；
(a2) metal molybdenum target is placed in magnetron sputtering chamber, the purity of the metal molybdenum target is 99.99%；
(a3) soda lime glass substrates clean in step (a1) on substrate pallet and are transferred to metal molybdenum target Magnetron sputtering chamber is evacuated to 1 × 10-4-9×10-4Pa, molybdenum target are 3-10cm, underlayer temperature at a distance from soda lime glass substrates It is 250 DEG C -500 DEG C, substrate is rotated with the speed of 5A/s to guarantee that sample is uniform when sputtering；
(a4) when sputtering power is 100-200W, the double-deck molybdenum film structure is prepared by controlling the air pressure of argon gas, it is first First in the case where argon gas is 2.0-3.5Pa, sputtering 5-15min obtains the first molybdenum layer with a thickness of 350-450nm, is then in argon gas 10-20min acquisition is sputtered under 0.15-0.30Pa with a thickness of the second molybdenum layer of 750-850nm；
(b) the metallic antimony film Sb/Mo/SLG along<003>orientation is prepared on the basis of step (a):
(b1) N is passed through to sputtering chamber2To atmospheric pressure, sputtering chamber is opened, changes metal molybdenum target into antimony target, the antimony target purity It is 99.99%；
(b2) repeat the above steps the operation of (a3)；
(b3) it is 30-100W in sputtering power, argon gas is sputtered when being 0.25Pa, and the sputtering thickness of antimony is about 300- 1000nm；
(c) finally by the metallic antimony film Sb/Mo/SLG of edge<003>orientation prepared in step (b) be put into vacuum degree be 1 × 10-4It is 1.5~3 addition selenium in the quartz ampoule of Pa and by Se/Sb the mass ratio of the material, antimony film is completely converted into Sb2Se3；Then quartz ampoule is transferred in Muffle furnace and carries out calcination process, obtains the antimony selenide along<002>direction preferential growth Optoelectronic film.
Further, when the first molybdenum layer is 400nm in step (a4), sputtering power 100W, argon gas 3.0Pa, sputtering 10min, when the second molybdenum layer is 800nm, sputtering power 100W, argon gas 0.25Pa sputter 15min.
Further, Se/Sb the mass ratio of the material is 2 in step (c).
Further, in step (c) maturing temperature be 250 DEG C -400 DEG C, heating rate be 5 DEG C/min, sintering time be 2~ 8h。
Further, sintering temperature is 325 DEG C in step (c).
It is compared with the prior art, the invention has the following beneficial effects:
The present invention utilizes Sb2Se3Material is helped from<002>direction growth tendency with higher by Sb<003> In further suppressing Sb2Se3Film and is sintered in sealed silica envelope and is also beneficial in the growth rate of other crystal orientation Sb2Se3The antimony selenide photoelectricity for having prepared a kind of edge<002>direction preferential growth along<002>direction height preferential growth is thin Film.The common inducing action of this three makes the selenizing Sb film prepared using method of the invention along the current-carrying in<002>direction Son has highest mobility, so as to which optical electro-chemistry hydrogen generation efficiency is greatly improved, has in optical electro-chemistry field and widely answers Use potentiality.
Detailed description of the invention
Fig. 1 is the selenizing Sb film direction of growth and carrier transport relational graph；
Fig. 2 is Sb2Se3Sb<003>/Mo substrate XRD spectra of growth；
Fig. 3 is the XRD spectra of antimony selenide powder and the selenizing Sb film prepared using method of the invention；
Fig. 4 is the SEM figure of the selenizing Sb film cross section prepared using method of the invention；
Fig. 5 is Sb2Se3The marcotexture of film；
Fig. 6 is the SEM figure of the antimony selenide film surface depositing platinum nanoparticles prepared using method of the invention；
Fig. 7 is the optoelectronic pole pictorial diagram (a) and photoelectrode structure figure (b) that the present invention makes；
Fig. 8 is that the linear volt-ampere for the optical electro-chemistry production hydrogen test that the selenizing Sb film prepared using the method for the present invention is carried out is swept Tracing.
Specific embodiment
The method of the present invention is described in detail with attached drawing combined with specific embodiments below.The magnetron sputtering that this experiment uses Instrument model is pulse laser deposition-magnetron sputtering composite system that manufacture is tieed up in Dalian together.Target device is Ke Telai Cisco M2AM10, magnetron sputtering DC power supply are that match grace thinks SI-DC500C.
One, Sb is prepared2Se3(002)/Mo/SLG selenizing Sb film
Embodiment 1
A kind of preparation method of the antimony selenide optoelectronic film of edge<002>direction preferential growth, includes the following steps:
(a) Mo/SLG conductive film is prepared:
(a1) successively it is cleaned by ultrasonic soda lime glass substrates with acetone, alcohol and deionized water, taking-up is immersed in alcohol Glass substrate is cleaned, when use is dried up with hair dryer；
(a2) metal molybdenum target is placed in magnetron sputtering chamber, the purity of the metal molybdenum target is 99.99%；
(a3) soda lime glass substrates clean in step (a1) on substrate pallet and are transferred to metal molybdenum target Magnetron sputtering chamber is evacuated to 1 × 10-4Pa, molybdenum target are 10cm at a distance from soda lime glass substrates, and underlayer temperature is 250 DEG C, are splashed Substrate is rotated with the speed of 5A/s to guarantee that sample is uniform when penetrating；
(a4) when sputtering power is 100W, the double-deck molybdenum film structure is prepared by controlling the air pressure of argon gas, is existed first Argon gas is the first molybdenum layer that sputtering 5min obtains with a thickness of 350nm under 3.5Pa, and then in the case where argon gas is 0.3Pa, sputtering 10min is obtained Obtain the second molybdenum layer with a thickness of 750nm；
(b) the metallic antimony film Sb/Mo/SLG along<003>orientation is prepared on the basis of step (a):
(b1) N is passed through to sputtering chamber2To atmospheric pressure, sputtering chamber is opened, changes metal molybdenum target into antimony target, the antimony target purity It is 99.99%；
(b2) repeat the above steps the operation of (a3)；
(b3) it is 30W in sputtering power, argon gas is sputtered when being 0.25Pa, and the sputtering of antimony is with a thickness of 300nm；
(c) finally by the metallic antimony film Sb/Mo/SLG of edge<003>orientation prepared in step (b) be put into vacuum degree be 1 × 10-4It is 1.5 addition selenium in the quartz ampoule of Pa and by Se/Sb the mass ratio of the material, antimony film is allowed to be completely converted into Sb2Se3；With Quartz ampoule is transferred in Muffle furnace afterwards and carries out calcination process, maturing temperature is 250 DEG C, and heating rate is 5 DEG C/min, when sintering Between be 2h, obtain the antimony selenide optoelectronic film along<002>direction preferential growth.
Embodiment 2
A kind of preparation method of the antimony selenide optoelectronic film of edge<002>direction preferential growth, includes the following steps:
(a) Mo/SLG conductive film is prepared:
(a1) successively it is cleaned by ultrasonic soda lime glass substrates with acetone, alcohol and deionized water, taking-up is immersed in alcohol Glass substrate is cleaned, when use is dried up with hair dryer；
(a2) metal molybdenum target is placed in magnetron sputtering chamber, the purity of the metal molybdenum target is 99.99%；
(a3) soda lime glass substrates clean in step (a1) on substrate pallet and are transferred to metal molybdenum target Magnetron sputtering chamber is evacuated to 4 × 10-4Pa, molybdenum target are 4cm at a distance from soda lime glass substrates, and underlayer temperature is 250 DEG C, are splashed Substrate is rotated with the speed of 5A/s to guarantee that sample is uniform when penetrating；
(a4) when sputtering power is 100W, the double-deck molybdenum film structure is prepared by controlling the air pressure of argon gas, is existed first Argon gas is the first molybdenum layer that sputtering 10min obtains with a thickness of 400nm under 3.0Pa, then sputters 15min in the case where argon gas is 0.25Pa Obtain the second molybdenum layer with a thickness of 800nm；
(b) the metallic antimony film Sb/Mo/SLG along<003>orientation is prepared on the basis of step (a):
(b1) N is passed through to sputtering chamber2To atmospheric pressure, sputtering chamber is opened, changes metal molybdenum target into antimony target, the antimony target purity It is 99.99%；
(b2) repeat the above steps the operation of (a3)；
(b3) it is 40W in sputtering power, argon gas is sputtered when being 0.25Pa, and the sputtering of antimony is with a thickness of 400nm；
(c) finally by the metallic antimony film Sb/Mo/SLG of edge<003>orientation prepared in step (b) be put into vacuum degree be 1 × 10-4It is 2 addition selenium in the quartz ampoule of Pa and by Se/Sb the mass ratio of the material, so that antimony film is completely converted into Sb2Se3；Then by stone English pipe, which is transferred in Muffle furnace, carries out calcination process, and maturing temperature is 325 DEG C, and heating rate is 5 DEG C/min, and sintering time is 6h obtains the antimony selenide optoelectronic film along<002>direction preferential growth.
Embodiment 3
A kind of preparation method of the antimony selenide optoelectronic film of edge<002>direction preferential growth, includes the following steps:
(a) Mo/SLG conductive film is prepared:
(a1) successively it is cleaned by ultrasonic soda lime glass substrates with acetone, alcohol and deionized water, taking-up is immersed in alcohol Glass substrate is cleaned, when use is dried up with hair dryer；
(a2) metal molybdenum target is placed in magnetron sputtering chamber, the purity of the metal molybdenum target is 99.99%；
(a3) soda lime glass substrates clean in step (a1) on substrate pallet and are transferred to metal molybdenum target Magnetron sputtering chamber is evacuated to 9 × 10-4Pa, molybdenum target are 3cm at a distance from soda lime glass substrates, and underlayer temperature is 500 DEG C, are splashed Substrate is rotated with the speed of 5A/s to guarantee that sample is uniform when penetrating；
(a4) when sputtering power is 200W, the double-deck molybdenum film structure is prepared by controlling the air pressure of argon gas, is existed first Argon gas is the first molybdenum layer that sputtering 15min obtains with a thickness of 450nm under 2.0Pa, then sputters 20min in the case where argon gas is 0.15Pa Obtain the second molybdenum layer with a thickness of 850nm；
(b) the metallic antimony film Sb/Mo/SLG along<003>orientation is prepared on the basis of step (a):
(b1) N is passed through to sputtering chamber2To atmospheric pressure, sputtering chamber is opened, changes metal molybdenum target into antimony target, the antimony target purity It is 99.99%；
(b2) repeat the above steps the operation of (a3)；
(b3) it is 100W in sputtering power, argon gas is sputtered when being 0.25Pa, and the sputtering of antimony is with a thickness of 1000nm；
(c) finally by the metallic antimony film Sb/Mo/SLG of edge<003>orientation prepared in step (b) be put into vacuum degree be 1 × 10-4It is 1.5 addition selenium in the quartz ampoule of Pa and by Se/Sb the mass ratio of the material, so that antimony film is completely converted into Sb2Se3；Then will Quartz ampoule, which is transferred in Muffle furnace, carries out calcination process, and maturing temperature is 400 DEG C, and heating rate is 5 DEG C/min, and sintering time is 8h obtains the antimony selenide optoelectronic film along<002>direction preferential growth.
Two, Sb2Se3<002>performance test of/Mo/SLG selenizing Sb film
1, the direction of growth of selenizing Sb film
The direction of growth of antimony selenide and the transport efficiency of carrier are closely related.As shown in Figure 1, if film is ribbon It is<hk0>that unit, which is parallel to the substrate surface i.e. direction of growth, and the transport efficiency of film is minimum, because carrier is needed in ribbon Between Robert Van de Walle's key in hop transmission；If film is grown along c- axis, that is, ribbon unit and substrate transverse, that Film will have highest transport efficiency, because carrier is transported along covalent bond direction always, have higher mobility； If the direction of growth is that ribbon and substrate are at an acute angle, transport efficiency is that the bigger angle the higher, and is all higher than in parallel to life It is long, it but is below the growth of c- axis.
2, x-ray diffractometer (XRD) is tested
Fig. 2 is Sb2Se3Sb<003>/Mo substrate XRD spectra of growth, from figure it is found that Sb film in Sb<003>/Mo There is very strong preferred orientation to grow in<003>direction, this is conducive to Sb in selenizing2Se3It is grown along<002>direction.Fig. 3 is powder The XRD spectra of last antimony selenide and the selenizing Sb film prepared using method of the invention, it can be seen that powder Sb2Se3< The peak intensity in 002 > direction is markedly less than Sb2Se3Film is edge which reflects the film direction of growth in the peak intensity in<002>direction The growth of<002>direction, and have very strong orientation because<002>peak be in the powder sample of No yield point it is weaker, But but becoming strongest in the film of preferred orientation, this also just demonstrates the present invention and has successfully synthesized height edge <002>the antimony selenide optoelectronic film of preferential growth.
3、Sb2Se3The marcotexture of film is tested
Fig. 4 is Sb2Se3The texture of film is tested, and the spatial distribution of preferred orientation can be intuitively reacted.It can be with from figure See Sb2Se3Film really in substrate normal direction along<002>to oriented growth, and main growth distribution is in the folder of substrate normal direction Angle is within 10 ° (Fig. 1, corresponding θ > 80 ° are shown in angle definition).This illustrates Sb2Se3Film is that height is raw along<002>preferred orientation Long.
4, scanning electron microscope (SEM) is tested
Fig. 5 is the SEM figure of the selenizing Sb film cross section prepared using method of the invention, it can be seen from the figure that molybdenum For double-layer structure, the film conductivity that the molybdenum of double-layer structure is prepared is more preferable, and corrosion resistance is also stronger；Simultaneously it is also seen that most The Sb on upper layer2Se3The double-deck molybdenum deposited with lower layer contacts well, this facilitates carrier and transmits to back electrode.
Three, the application along the antimony selenide optoelectronic film of<002>direction preferential growth in terms of optical electro-chemistry produces hydrogen
The test of optical electro-chemistry H2-producing capacity is carried out to the selenizing Sb film of prepared c- axis preferential growth, first in selenium Changing deposition on Sb film surface facilitates the nano platinum particle that water is reduced to hydrogen, as a result as shown in fig. 6, can be with from SEM figure Find out that there is high-visible Pt nanoparticle on the surface of selenizing Sb film；The antimony selenide of Pt nanoparticle will be deposited again Film is fabricated to optoelectronic pole material, and Fig. 7 gives the optoelectronic pole pictorial diagram (a) made and photoelectrode structure figure (b)；Finally exist (100mW/cm under the irradiation of standard sunlight2), the test of optical electro-chemistry H2-producing capacity, knot have been carried out in the sulfuric acid electrolyte of 1mol/L Fruit using the optoelectronic pole of the selenizing Sb film production of c- axle preferrel orientation growth as shown in figure 8, it can be seen from the figure that had very High production hydrogen photoelectric current is 25.2mA/cm2, this is mainly due to selenizing Sb films prepared by the present invention to have high c- axis preferentially Oriented growth, and along the carrier in<002>direction there is highest mobility to finally improve to promote the progress of reaction Produce hydrogen photoelectric current.
Reaction mechanism: this is mainly due to Sb2Se3Material from c- axis direction growth tendency with higher, and Sb < 003 > help to further suppress Sb2Se3Film other crystal orientation growth rate, this is because the Sb presoma of preferred orientation Film is conducive to keep the direction of microstress constant in selenidation process, and there are big cellular structures to be conducive to Se for Sb membrane structure It diffuses into Sb film while reacting, finally make Sb2Se3Along<002>direction height preferential growth；In addition, in sealing quartz Sintering is also beneficial to Sb in pipe2Se3Along<002>direction height preferential growth, this is because Se can be kept during the sintering process Saturated vapor pressure is constant to be conducive to preferential growth, and promotes Se to expand at a lower reaction temperature to Sb film by increasing Se partial pressure It dissipates and reacts generation antimony selenide.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (5)

1. a kind of preparation method of the antimony selenide optoelectronic film of edge<002>direction preferential growth, which is characterized in that including walking as follows It is rapid:
(a) Mo/SLG conductive film is prepared:
(a1) successively it is cleaned by ultrasonic soda lime glass substrates with acetone, alcohol and deionized water, and is immersed in alcohol, when use is used Hair dryer drying；
(a2) metal molybdenum target is placed in magnetron sputtering chamber, the purity of the metal molybdenum target is 99.99%；
(a3) soda lime glass substrates clean in step (a1) on substrate pallet and are transferred to the magnetic control with metal molybdenum target Sputtering chamber is evacuated to 1 × 10-4-9×10-4Pa, molybdenum target are 3-10cm at a distance from soda lime glass substrates, and underlayer temperature is 250 DEG C -500 DEG C, substrate is rotated with the speed of 5A/s to guarantee that sample is uniform when sputtering；
(a4) when sputtering power is 100-200W, the double-deck molybdenum film structure is prepared by controlling the air pressure of argon gas, is existed first Argon gas is the first molybdenum layer that sputtering 5-15min obtains with a thickness of 350-450nm under 2.0-3.5Pa, is then 0.15- in argon gas 10-20min acquisition is sputtered under 0.30Pa with a thickness of the second molybdenum layer of 750-850nm；
(b) the metallic antimony film Sb/Mo/SLG along<003>orientation is prepared on the basis of step (a):
(b1) N is passed through to sputtering chamber2To atmospheric pressure, sputtering chamber is opened, changes metal molybdenum target into antimony target, the antimony target purity is 99.99%；
(b2) repeat the above steps the operation of (a3)；
(b3) it is 30-100W in sputtering power, argon gas is sputtered when being 0.25Pa, and the sputtering thickness of antimony is about 300- 1000nm；
(c) the metallic antimony film Sb/Mo/SLG of edge<003>orientation prepared in step (b) is finally put into vacuum degree is 1 × 10- 4It is 1.5~3 addition selenium in the quartz ampoule of Pa and by Se/Sb the mass ratio of the material, antimony film is allowed to be completely converted into Sb2Se3；With Quartz ampoule is transferred in Muffle furnace afterwards and carries out calcination process, obtains the antimony selenide optoelectronic film along<002>direction preferential growth.
2. the preparation method of the antimony selenide optoelectronic film of edge<002>direction according to claim 1 preferential growth, feature It is, when the first molybdenum layer is 400nm in step (a4), sputtering power 100W, argon gas 3.0Pa sputter 10min, the second molybdenum When layer is 800nm, sputtering power 100W, argon gas 0.25Pa sputter 15min.
3. the preparation method of the antimony selenide optoelectronic film of edge<002>direction according to claim 1 preferential growth, feature It is, Se/Sb the mass ratio of the material is 2 in step (c).
4. the preparation method of the antimony selenide optoelectronic film of edge<002>direction according to claim 1 preferential growth, feature It is, maturing temperature is 250 DEG C -400 DEG C in step (c), and heating rate is 5 DEG C/min, and sintering time is 2~8h.
5. the preparation method of the antimony selenide optoelectronic film of edge<002>direction according to claim 4 preferential growth, feature It is, sintering temperature is 325 DEG C in step (c).
CN201910012399.8A 2019-01-07 2019-01-07 Preparation method of antimony selenide photoelectric film preferentially growing along (002) direction Expired - Fee Related CN109518149B (en)

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CN112376113A (en) * 2020-10-28 2021-02-19 河南大学 Antimony selenide crystal, preparation method and application thereof

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CN111020487A (en) * 2019-11-21 2020-04-17 华中科技大学 Method for preparing film of quasi-one-dimensional structure material with controllable orientation
CN112376113A (en) * 2020-10-28 2021-02-19 河南大学 Antimony selenide crystal, preparation method and application thereof
CN112376113B (en) * 2020-10-28 2022-02-11 河南大学 Antimony selenide crystal, preparation method and application thereof

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