CN106927688A - A kind of halogen doping ZnMgO films and preparation method thereof - Google Patents
A kind of halogen doping ZnMgO films and preparation method thereof Download PDFInfo
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- CN106927688A CN106927688A CN201710165933.XA CN201710165933A CN106927688A CN 106927688 A CN106927688 A CN 106927688A CN 201710165933 A CN201710165933 A CN 201710165933A CN 106927688 A CN106927688 A CN 106927688A
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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- H10N30/00—Piezoelectric or electrostrictive devices
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
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- C03C2217/228—Other specific oxides
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
Abstract
The invention belongs to low-dimension nano material and field of nanometer technology, it is proposed that a kind of halogen doping ZnMgO films and preparation method thereof.The preparation method comprises the following steps：By substrate cleaning, drying；By in two water zinc acetates and magnesium source addition solvent, the solvent is EGME or normal propyl alcohol, and stabilizer uses monoethanolamine, and 1~2h is stirred at 55~80 DEG C, obtains solution；Then by NH4X or NaX is added in solution, and wherein X represents halogen, and 2~3h is stirred at 55~80 DEG C, obtains the colloidal sol of stable homogeneous；Substrate prepares film and circulates for several times using spin-coating method；The substrate that growth has film is annealed in being put into heat-treatment furnace, and annealing temperature is 400~700 DEG C, and soaking time is 0.5~3h；Room temperature is subsequently cooled to, the ZnMgO films of halogen doping are obtained.Gentle, low cost that halogen doping ZnMgO films of the present invention are that one kind prepares environment, reliability is high and preparation method of process is simple, and the method is expected to obtain the thin-film material with piezoelectric property.
Description
Technical field
The invention belongs to low-dimension nano material field, especially by halogen doping ZnMgO films and preparation method thereof.
Background technology
The ZnMgO of wurtzite structure is a kind of direct band gap wide bandgap semiconductor material with piezoelectricity and photoelectric characteristic
Material, the hexagonal wurtzite structure with standard.As a kind of typical luminescent material, in the shortwave long hair such as blue green light, ultraviolet light
Light source aspect has obvious advantage, can be used to prepare various luminescent devices, such as planar optical waveguide, transparency electrode, ultraviolet light
Detector, ultraviolet light emitting device etc..But, with the development of science and technology, people improve constantly to the application requirement of device, ZnMgO
Also increasingly manifest in many deficiencies of application aspect, such as exciton bind energy not enough big, band gap is not wide enough.ZnMgO not only has
The crystal structure similar to zinc oxide and optical property, and its band structure can arbitrarily change within the specific limits.In recent years,
Mg causes people and widely pays close attention to by the ZnMgO materials that alloying is obtained.What the difference according to Mg solid solubility was formed
Zn1-xMgxThe energy gap of O alloys can between 3.37-7.8eV continuously adjustabe.Research is shown, is obtained by alloying
Piezoelectric modulus increase after ZnMgO.As a kind of ternary crystalline material, ZnMgO have good optics, piezoelectricity, photosensitive, air-sensitive,
The characteristics such as photocatalysis, conductance.
The performance of ZnMgO is influenceed by Mg solid solubility sizes, and when Mg contents are more in raw material, Mg contents can be limited to metal
The solid solubility of element.In view of this factor, we can be modified using nonmetal doping to ZnMgO.Halogen family unit
The plain dopant as ZnMgO, their doping instead of the position of O in ZnMgO.Due to band structure in, valence band is main
It is made up of the 2p tracks of O, is mainly when VII race's element ion occupies lattice point in displacement form and perturbation is produced to valence band, and it is right
The disturbance of conduction band electron is smaller, that is, relatively small to the scattering process of electron transfer, be so conducive to common bluebeard obtain mobility compared with
Doping film high.Due to there is larger electronegativity and size difference between halogen and O atom, it is contemplated that compression is stretched
Lattice strain, it will the piezoelectric property of strong influence ZnMgO.
But, current relatively effective use magnetron sputtering method, the chemical vapour deposition technique for realizing that nonmetal doping is more
Deng.These methods are generally required under vacuum conditions or completed under hyperbaric environment, and its preparation technology level is higher, and repeatability is not
It is high that its is costly.Sol-gal process is a kind of temperature that can on different substrates prepare thin-film material and only need to be relatively low
Degree, its preparation method is simple.Form low viscous because raw material used in sol-gal process is dispersed in solvent first
Solution, accordingly, it is possible to the uniformity of molecular level is obtained in a short period of time, when gel is formed, between reactant very
It is probably to be uniformly mixed on a molecular scale.Due to by solution reaction step, then mix with being just easy to equal and quantitative
Enter some elements, realize the Uniform Doped on molecular level.Halogen doping ZnMgO films are realized by sol-gal process, in fact
Matter is that the lattice strain of the common initiation of metal ion and nonmetallic ion can change the property of material, and it has a wide range of applications
Prospect, is expected to obtain the thin-film material with piezoelectric property.
The content of the invention
It is an object of the invention to provide a kind of halogen doping ZnMgO films and preparation method thereof, the method prepares environment temperature
With, low cost, reliability is high and process is simple, and the method is expected to obtain the thin-film material with piezoelectric property.
To achieve the above object, the technical solution used in the present invention is：A kind of halogen doping ZnMgO films (one kind pressure
Conductive film), it is characterised in that obtained by following steps：
(1) substrate is immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with supersonic cleaning machine ultrasound 15~
35min is simultaneously dried with infrared lamp；The substrate is Si pieces or quartz glass plate；
(2) by two water zinc acetates and magnesium source addition solvent, the solvent is EGME or normal propyl alcohol, and stabilizer is adopted
With monoethanolamine, 1~2h is stirred at 55~80 DEG C, obtain solution；Then by NH4X or NaX is added in solution, and wherein X represents halogen
Element, stirs 2~3h at 55~80 DEG C, obtains colloidal sol；
(3) substrate that will be treated in step (1) is placed on the estrade of photoresist spinner, by the colloidal sol in step (2) using getting rid of
Glue machine, then rotates 30s~60s so that colloidal sol is uniformly distributed on substrate under 2000~5000rpm speed, and 150~
Colloidal sol is dried at 300 DEG C；
(4) and then on the estrade of the placement photoresist spinner of the substrate with colloidal sol, the colloidal sol in step (2) is used into photoresist spinner,
30s~60s is rotated under 2000~5000rpm speed so that colloidal sol is uniformly distributed on substrate, colloidal sol is dried at 150~300 DEG C
It is dry；This step is repeatedly circulated, obtains growing the substrate for having film；
(5) substrate that growth in step (4) has film is put into heat-treatment furnace and is annealed, annealing temperature is 400~700
DEG C, soaking time is 0.5~3h；Room temperature is subsequently cooled to, halogen doping ZnMgO films are obtained.
The preparation method of above-mentioned a kind of halogen doping ZnMgO films, it is characterised in that comprise the following steps：
(1) substrate is immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with supersonic cleaning machine ultrasound 15~
35min simultaneously dries the { pretreatment of substrate with infrared lamp.Main purpose is thoroughly to remove dust, the greasy dirt on surface etc., to strengthen
Adhesive ability between substrate and film }；The substrate is Si pieces or quartz glass plate；
(2) in two water zinc acetates and magnesium source (magnesium source is the one kind in four water magnesium acetates, magnesium chloride etc.) being added into solvent, institute
Solvent is stated for EGME, stabilizer uses monoethanolamine, 1~2h is stirred at 55~80 DEG C, obtain solution；Then by NH4X
Or in NaX addition solution, wherein X represents halogen, and 2~3h is stirred at 55~80 DEG C, the colloidal sol { selection two of stable homogeneous is obtained
Water acetic acid zinc [Zn (CH3COO)2·2H2O] as presoma, EGME [C3H8O2] and monoethanolamine [C2H7NO] it is used separately as
Solvent, stabilizer, doped source is by four water magnesium acetate [Mg (CH3COO)2·4H2O] and NH4X (X represents halogen) is provided }；
(3) substrate that will be treated in step (1) is placed on the estrade of photoresist spinner, by the colloidal sol in step (2) using getting rid of
Glue machine, then rotates 30s~60s so that colloidal sol is uniformly distributed on substrate under 2000~5000rpm speed, and 150~
Colloidal sol is dried at 300 DEG C；
(4) and then the substrate with colloidal sol is placed on the estrade of photoresist spinner, by the thin of the Mg in step (2) and halogen doping
Film sol uses photoresist spinner, 30s~60s is then rotated under 2000~5000rpm speed so that colloidal sol uniformly divides on substrate
Cloth, and dry colloidal sol at 150~300 DEG C；Repeatedly circulate this step and { this step is circulated more than 10 times, by place in step (1)
The substrate managed prepares film and circulates for several times using spin-coating method }, obtain growing the substrate for having film；Repeatedly circulating this step makes
The thickness of film is 200nm~800nm；
(5) substrate that growth in step (4) has film is put into heat-treatment furnace and is annealed, annealing temperature is 400~700
DEG C, soaking time is 0.5~3h；Room temperature is subsequently cooled to, halogen doping ZnMgO films are obtained.
In the step (2), by formula Zn1-mMgmO:nX；Wherein X represents halogen, and the span of m is 0.05~0.3,
The span of n is 0.01~0.3, chooses two water zinc acetates, magnesium source and NH4It is a kind of in X or NaX；By Zn in colloidal sol2+、Mg2+
Concentration [Zn2++Mg2+]:Molar concentration rate=the 0.99-1.01 of monoethanolamine (MEA), chooses monoethanolamine (MEA)；By two water acetic acid
Zinc, EGME are 0.1~0.5mol/L as solute and solvent configuration concentration, choose EGME.
In the step (2), two water zinc acetates, magnesium source, solvent, the proportioning of monoethanolamine are：1.5521g-2.1064g:
0.1083g-0.6498g:50ml:0.98mL, chooses two water zinc acetates, magnesium source, solvent, monoethanolamine；By formula Zn1-mMgmO:
nX；Wherein X represents halogen, and the span of m is that the span of 0.05~0.3, n is 0.01~0.3, chooses NH4X or NaX
Middle one kind.
The present invention is to realize halogen to ZnMgO film dopings by sol-gal process, is to combine halogen and sol-gal process
The characteristics of a kind of simple possible for arriving halogen doping ZnMgO films preparation method.The present invention uses sol-gal process, can
Even film layer, the thin-film material that compactness is good and film thickness is controllable are prepared on substrate, just can be with benign environment
Complete halogen to adulterate ZnMgO, simplify preparation technology, and with obvious repeatability and stability.
The beneficial effects of the present invention are：
1st, preparation flow of the present invention is simple, shortens preparation process cycle, efficiency high；
2nd, the present invention, while preparation temperature is relatively low, reduces production cost without carrying out under vacuum conditions；
3rd, the present invention is easily controlled to the doping of halogen, and with obvious stability and repeatability, and energy
Produce have good uniformity, the thin-film material that compactness is good, thickness is controllable.
4th, the property of material can be changed its essence is the lattice strain of the common initiation of metal ion and nonmetallic ion, its
Have a wide range of applications, be expected to obtain the thin-film material with piezoelectric property.
Brief description of the drawings
Fig. 1 is ZnMgO film XRD spectrum of the present invention through different halogen dopings.
Fig. 2 is Cl of the present invention‐Adulterate the UV, visible light transmitted spectrum of different ZnMgO films.
Fig. 3 is various concentrations Cl of the present invention‐Doping ZnMgO film UV, visible light transmitted spectrums.
Fig. 4 is the UV, visible light transmitted spectrum of difference halogen doping ZnMgO films of the invention.
Specific embodiment
To make present disclosure, technical scheme and advantage become more apparent, below in conjunction with the drawings and specific embodiments
The present invention is expanded on further, these embodiments are merely to illustrate the present invention, and the present invention is not limited only to following examples.
Embodiment 1
A kind of preparation method of halogen doping ZnMgO films, comprises the following steps：
1) Si pieces or quartz glass plate are immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with ultrasonic cleaning
Machine ultrasound 15min is simultaneously dried with infrared lamp；
2) by the four water magnesium acetate solid dissolvings of the acetic acid dihydrate zinc of 2.1064g and 0.1083g in the ethylene glycol of 50ml
In methyl ether solution, 0.98mL monoethanolamines (MEA) are added so that Zn in solution2+、Mg2+Concentration [Zn2++Mg2+]:Monoethanolamine
(MEA) molar concentration rate ≈ 1, is then placed into being sufficiently stirred for above constant temperature blender with magnetic force.Wherein temperature setting exists
70 DEG C, soaking time is 1 hour, obtains Zn0.95Mg0.05The colloidal sol of O, is subsequently adding the NH of 0.01mol4X (X represents halogen,
Such as the one kind in F, Cl, Br, I), and continue to stir 2h, realize doping of the halogen to ZnMgO.Deng stirring fully after be cooled to room
The vitreosol that cation concn is 0.2mol/L is obtained after the filtering of Wen Zaijing filter papers, placing after 24h is fully aged to be carried out
Rejection film.
3) the Si pieces or quartz glass plate that will be treated in step (1) are placed on the estrade of photoresist spinner, by step 2) in
Colloidal sol use photoresist spinner, then under 3500rpm speed rotate 30s~60s so that colloidal sol is in Si pieces or quartz glass plate
On be uniformly distributed, and colloidal sol is dried at 150~300 DEG C；
4) Si pieces and then with colloidal sol or quartz glass plate piece are placed on the estrade of photoresist spinner, by step 2) in it is molten
The film of glue Mg and halogen doping uses photoresist spinner, 30s~60s is then rotated under 3500rpm speed so that colloidal sol is in Si pieces
Or be uniformly distributed on quartz glass plate, and dry colloidal sol at 150~300 DEG C；Circulate this step more than 10 times；Make film
Thickness be 200nm~800nm；
5) Si pieces or quartz glass plate that growth in step (4) has film are put into heat-treatment furnace and are annealed, annealing temperature
It is 400~700 DEG C to spend, and soaking time is 1h；Room temperature is subsequently cooled to, the ZnMgO films of halogen doping are obtained.
Embodiment 2 (being comparison example)：
A kind of preparation method of halogen doping ZnMgO films, comprises the following steps：
1) Si pieces or quartz glass plate are immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with ultrasonic cleaning
Machine ultrasound 15min is simultaneously dried with infrared lamp；
2) by the four water magnesium acetate solid dissolvings of the acetic acid dihydrate zinc of 2.1064g and 0.1083g in the ethylene glycol of 50ml
In methyl ether solution, 0.98mL monoethanolamines (MEA) are added so that Zn in solution2+:The molar concentration rate ≈ 1 of MEA, then places
It is sufficiently stirred for above constant temperature blender with magnetic force.Wherein at 70 DEG C, soaking time is 3h to temperature setting, is obtained
Zn0.95Mg0.05The colloidal sol of O, the doping of halogen is not used.Deng stirring fully after be cooled to room temperature again through filter paper filter after obtain
Cation concn is the vitreosol of 0.2mol/L, and placing after 24h is fully aged can carry out rejection film.
3) by step 1) in treat Si pieces or quartz glass plate place photoresist spinner estrade on, by step 2) in
Colloidal sol uses photoresist spinner, 30s~60s is then rotated under 3500rpm speed so that colloidal sol is on Si pieces or quartz glass plate
It is uniformly distributed, and dries colloidal sol at 150~300 DEG C；
4) Si pieces and then with colloidal sol or quartz glass plate piece are placed on the estrade of photoresist spinner, by step 2) in it is molten
Glue uses photoresist spinner, and 30s~60s is then rotated under 3500rpm speed so that colloidal sol is equal on Si pieces or quartz glass plate
Even distribution, and dry colloidal sol at 150~300 DEG C；Circulate this step more than 10 times；Make the thickness of film for 200nm~
800nm；
5) by step 4) in the growth Si pieces or quartz glass plate that have film be put into heat-treatment furnace and anneal, annealing temperature
It it is 400~700 DEG C, soaking time is 1h；Room temperature is subsequently cooled to, ZnMgO films are obtained.
Embodiment 3
A kind of preparation method of halogen doping ZnMgO films, comprises the following steps：
1) Si pieces or quartz glass plate are immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with ultrasonic cleaning
Machine ultrasound 15min is simultaneously dried with infrared lamp；
2) by 1.9956,1.7738, the acetic acid dihydrate zinc of 1.5521g respectively with 0.2166,0.4332,0.6498g
Four water magnesium acetate solid dissolvings add 0.98mL monoethanolamines (MEA) so that in solution in the EGME solution of 50ml
Zn2+、Mg2+Concentration [Zn2++Mg2+]:The molar concentration rate ≈ 1 of MEA, is then placed into being carried out above constant temperature blender with magnetic force fully
Stirring.It is each configured to Zn0.9Mg0.1O、Zn0.8Mg0.2O、Zn0.7Mg0.3Tri- kinds of colloidal sols of O, wherein temperature setting are incubated at 70 DEG C
Time is 1 hour, is then respectively adding the NH of 0.05mol4Cl, and continue to stir 2h, realize Cl‐Doping to ZnMgO.Deng
It is cooled to after stirring fully and the vitreosol that cation concn is 0.2mol/L is obtained after room temperature is filtered through filter paper again, is placed
24h can carry out rejection film after being fully aged.
3) the Si pieces or quartz glass plate that will be treated in step (1) are placed on the estrade of photoresist spinner, by step 2) in
Colloidal sol use photoresist spinner, then under 3500rpm speed rotate 30s~60s so that colloidal sol is in Si pieces or quartz glass plate
On be uniformly distributed, and colloidal sol is dried at 150~300 DEG C；
4) Si pieces and then with colloidal sol or quartz glass plate piece are placed on the estrade of photoresist spinner, by step 2) in it is molten
The film of glue Mg and halogen doping uses photoresist spinner, 30s~60s is then rotated under 3500rpm speed so that colloidal sol is in Si pieces
Or be uniformly distributed on quartz glass plate, and dry colloidal sol at 150~300 DEG C；Circulate this step more than 10 times；Make film
Thickness be 200nm~800nm；
5) by step 4) in the growth Si pieces or quartz glass plate that have film be put into heat-treatment furnace and anneal, annealing temperature
It it is 400~700 DEG C, soaking time is 1h；Room temperature is subsequently cooled to, Cl is obtained‐The ZnMgO films of doping.
Embodiment 4
A kind of preparation method of halogen doping ZnMgO films, comprises the following steps：
1) Si pieces or quartz glass plate are immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with ultrasonic cleaning
Machine ultrasound 35min is simultaneously dried with infrared lamp；
2) by the acetic acid dihydrate zinc of 1.7738g respectively with the four water magnesium acetate solid dissolvings of 0.4332g in the second of 50ml
In glycol methyl ether solution, 0.98mL monoethanolamines (MEA) are added so that Zn in solution2+、Mg2+Concentration [Zn2++Mg2+]:MEA's
Molar concentration rate ≈ 1, is then placed into being sufficiently stirred for above constant temperature blender with magnetic force.It is configured to Zn0.8Mg0.2O colloidal sols, its
At 70 DEG C, soaking time is 1 hour to middle temperature setting, be then respectively adding 0.01mol, 0.05mol, 0.1mol, 0.2mol,
The NH of 0.3mol4Cl, and continue to stir 2h, realize Cl‐Doping to ZnMgO.Deng stirring fully after be cooled to room temperature again through filtering
The vitreosol that cation concn is 0.2mol/L is obtained after paper filtering, placing after 24h is fully aged can carry out rejection film.
3) the Si pieces or quartz glass plate that will be treated in step (1) are placed on the estrade of photoresist spinner, by step 2) in
Colloidal sol use photoresist spinner, then under 3500rpm speed rotate 30s~60s so that colloidal sol is in Si pieces or quartz glass plate
On be uniformly distributed, and colloidal sol is dried at 150~300 DEG C；
4) Si pieces and then with colloidal sol or quartz glass plate piece are placed on the estrade of photoresist spinner, by step 2) in it is molten
The film of glue Mg and halogen doping uses photoresist spinner, 30s~60s is then rotated under 3500rpm speed so that colloidal sol is in Si pieces
Or be uniformly distributed on quartz glass plate, and dry colloidal sol at 150~300 DEG C；Circulate this step more than 10 times；Make film
Thickness be 200nm~800nm；
5) by step 4) in the growth Si pieces or quartz glass plate that have film be put into heat-treatment furnace and anneal, annealing temperature
It it is 400~700 DEG C, soaking time is 1h；Room temperature is subsequently cooled to, the Cl of various concentrations is obtained‐The ZnMgO films of doping.
Embodiment 5
A kind of preparation method of halogen doping ZnMgO films, comprises the following steps：
1) Si pieces or quartz glass plate are immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with ultrasonic cleaning
Machine ultrasound 15min is simultaneously dried with infrared lamp；
2) by the acetic acid dihydrate zinc of 1.7738g respectively with the four water magnesium acetate solid dissolvings of 0.4332g in the second of 50ml
In glycol methyl ether solution, 0.98mL monoethanolamines (MEA) are added so that Zn in solution2+、Mg2+Concentration [Zn2++Mg2+]:MEA's
Molar concentration rate ≈ 1, is then placed into being sufficiently stirred for above constant temperature blender with magnetic force.It is configured to Zn0.8Mg0.2O colloidal sols, its
At 70 DEG C, soaking time is 1 hour to middle temperature setting, is then respectively adding the NH of 0.1mol4F、NH4Cl、NH4Br、NH4I shapes
In contrast with, and continue to stir 2h, realize doping of the halogen to ZnMgO.Deng stirring fully after be cooled to room temperature again through filter paper mistake
The vitreosol that cation concn is 0.2mol/L is obtained after filter, placing after 24h is fully aged can carry out rejection film.
3) the Si pieces or quartz glass plate that will be treated in step (1) are placed on the estrade of photoresist spinner, by step 2) in
Colloidal sol use photoresist spinner, then under 3500rpm speed rotate 30s~60s so that colloidal sol is in Si pieces or quartz glass plate
On be uniformly distributed, and colloidal sol is dried at 150~300 DEG C；
4) Si pieces and then with colloidal sol or quartz glass plate piece are placed on the estrade of photoresist spinner, by step 2) in it is molten
The film of glue Mg and halogen doping uses photoresist spinner, 30s~60s is then rotated under 3500rpm speed so that colloidal sol is in Si pieces
Or be uniformly distributed on quartz glass plate, and dry colloidal sol at 150~300 DEG C；Circulate this step more than 10 times；Make film
Thickness be 200nm~800nm；
5) Si pieces or quartz glass plate that growth in step (4) has film are put into heat-treatment furnace and are annealed, annealing temperature
It is 400~700 DEG C to spend, and soaking time is 0.5h；Room temperature is subsequently cooled to, the ZnMgO for obtaining the halogen doping of various concentrations is thin
Film.
Referring to accompanying drawing 1, Fig. 2, it is the XRD spectra drawn according to embodiment 1~2, and Fig. 1, Fig. 2 show, when to ZnMgO
During doping halogens, occur the strong of (002) peak after different degrees of skew, and doping when (002) peak is relative to undoped p
There is different degrees of change in degree and peak width；Even Fig. 1, Fig. 2 illustrate that a small amount of halogen successfully can be also mixed ZnMgO films
It is miscellaneous.
Fig. 3 is the UV, visible light transmitted light spectrogram of embodiment 3.Fig. 3 is under the conditions of same process, to be made on quartz glass
The Zn of standby Cl doping1-xMgxThe UV, visible light transmitted spectrum of O film samples, wherein x values are respectively x=0.1,0.2,0.3.It is first
First, there is transmission of visible light higher, transmissivity in the range of a length of 400nm~700nm of visible light wave as seen from Figure 3
All reach more than 80%, it may be said that to visible ray substantially transparent.And in the range of a length of 350nm~400nm of ultraviolet light wave, it is made
Standby Cl‐The Zn of doping1‐xMgxO is with Mg2+The increase of doping concentration, i.e. x=1 increase to 0.3, and the ABSORPTION EDGE of film sample is presented
Rule.
Fig. 4 is the UV, visible light transmitted light spectrogram of embodiment 4.Fig. 4 is under the conditions of same process, to be made on quartz glass
Standby various concentrations Cl‐The UV, visible light transmitted spectrum of the ZnMgO film samples of doping.The ZnMgO of undoped p has as seen from the figure
Visible light transmission rate higher, with Cl‐The raising of concentration, the transmissivity of thin-film material weakens into regularity, and with Cl‐Doping
The increase of concentration, ABSORPTION EDGE is moved to short long wave length direction, that is, occur moving to right.Prove the Cl of various concentrations‐It is successfully right
ZnMgO is doped.
In embodiment 5, the ZnMgO of different halogen dopings has visible light transmission rate higher, with different halogen dopings, film
The transmissivity of material weakens into regularity, and with the increase of F, Cl, Br, I doping concentration, ABSORPTION EDGE is moved to short long wave length direction
It is dynamic, that is, occur moving to right.Prove that different halogens are successfully doped to ZnMgO.
Embodiment 6
Essentially identical with embodiment 1, embodiment 3-5, difference is：Four water magnesium acetates are replaced by magnesium chloride, NH4X
Replaced by NaX, obtain halogen doping ZnMgO films.
The invention allows for a kind of piezoelectric membrane (a kind of halogen doping ZnMgO films), it uses any one as described above
Halogen doping ZnMgO films obtained in preparation method described in embodiment.
It should be noted that it will be understood by those within the art that, technical scheme can be carried out
Modification or equivalent, without deviating from the objective and scope of technical solution of the present invention, it all should cover will in right of the invention
Ask in the middle of scope.
Claims (6)
1. a kind of halogen doping ZnMgO films, it is characterised in that obtained by following steps：
(1) substrate is immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with 15~35min of supersonic cleaning machine ultrasound simultaneously
Dried with infrared lamp；The substrate is Si pieces or quartz glass plate；
(2) by two water zinc acetates and magnesium source addition solvent, the solvent is EGME or normal propyl alcohol, and stabilizer uses second
Hydramine, stirs 1~2h at 55~80 DEG C, obtains solution；Then by NH4X or NaX is added in solution, and wherein X represents halogen,
2~3h is stirred at 55~80 DEG C, colloidal sol is obtained；
(3) substrate that will be treated in step (1) is placed on the estrade of photoresist spinner, and the colloidal sol in step (2) is used into photoresist spinner,
Then 30s~60s is rotated under 2000~5000rpm speed so that colloidal sol is uniformly distributed on substrate, and at 150~300 DEG C
It is lower to dry colloidal sol；
(4) and then on the estrade of the placement photoresist spinner of the substrate with colloidal sol, the colloidal sol in step (2) is used into photoresist spinner, 2000
30s~60s is rotated under~5000rpm speed so that colloidal sol is uniformly distributed on substrate, colloidal sol is dried at 150~300 DEG C；
This step is repeatedly circulated, obtains growing the substrate for having film；
(5) substrate that growth in step (4) has film is put into heat-treatment furnace and is annealed, annealing temperature is 400~700 DEG C, is protected
The warm time is 0.5~3h；Room temperature is subsequently cooled to, halogen doping ZnMgO films are obtained.
2. a kind of preparation method of halogen doping ZnMgO films, it is characterised in that comprise the following steps：
(1) substrate is immersed in acetone, absolute ethyl alcohol, deionized water respectively, then with 15~35min of supersonic cleaning machine ultrasound simultaneously
Dried with infrared lamp；The substrate is Si pieces or quartz glass plate；
(2) by two water zinc acetates and magnesium source addition solvent, the solvent is EGME or normal propyl alcohol, and stabilizer uses second
Hydramine, stirs 1~2h at 55~80 DEG C, obtains solution；Then by NH4X or NaX is added in solution, and wherein X represents halogen,
2~3h is stirred at 55~80 DEG C, colloidal sol is obtained；
(3) substrate that will be treated in step (1) is placed on the estrade of photoresist spinner, and the colloidal sol in step (2) is used into photoresist spinner,
Then 30s~60s is rotated under 2000~5000rpm speed so that colloidal sol is uniformly distributed on substrate, and at 150~300 DEG C
It is lower to dry colloidal sol；
(4) and then on the estrade of the placement photoresist spinner of the substrate with colloidal sol, the colloidal sol in step (2) is used into photoresist spinner, 2000
30s~60s is rotated under~5000rpm speed so that colloidal sol is uniformly distributed on substrate, colloidal sol is dried at 150~300 DEG C；
This step is repeatedly circulated, obtains growing the substrate for having film；
(5) substrate that growth in step (4) has film is put into heat-treatment furnace and is annealed, annealing temperature is 400~700 DEG C, is protected
The warm time is 0.5~3h；Room temperature is subsequently cooled to, halogen doping ZnMgO films are obtained.
3. the preparation method of a kind of halogen doping ZnMgO films according to claim 2, it is characterised in that：The step
(2) in, by formula Zn1-mMgmO:nX；Wherein X represents halogen, and the span of m is that the span of 0.05~0.3, n is
0.01~0.3, choose two water zinc acetates, magnesium source and NH4It is a kind of in X or NaX；By Zn in colloidal sol2+、Mg2+Concentration [Zn2++Mg2 +]:Molar concentration rate=the 0.99-1.01 of monoethanolamine (MEA), chooses monoethanolamine (MEA)；By two water zinc acetates, EGME
It is 0.1~0.5mol/L as solute and solvent configuration concentration, chooses EGME.
4. the preparation method of a kind of halogen doping ZnMgO films according to Claims 2 or 3, it is characterised in that：Magnesium source is
One kind in four water magnesium acetates, magnesium chloride.
5. the preparation method of a kind of halogen doping ZnMgO films according to Claims 2 or 3, it is characterised in that：X be F,
One kind in Cl, Br, I.
6. the preparation method of a kind of halogen doping ZnMgO films according to claim 2, it is characterised in that：Prepared
The thickness of halogen doping ZnMgO films is 200nm~800nm.
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Cited By (2)
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| CN111785793A (en) * | 2020-08-11 | 2020-10-16 | 中国科学院长春光学精密机械与物理研究所 | ZnMgO ultraviolet detector and preparation method thereof |
| CN112563343A (en) * | 2020-12-09 | 2021-03-26 | 电子科技大学 | Based on Zn1-xMgxInorganic solar cell with O buffer layer and preparation method thereof |
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| CN111785793A (en) * | 2020-08-11 | 2020-10-16 | 中国科学院长春光学精密机械与物理研究所 | ZnMgO ultraviolet detector and preparation method thereof |
| CN112563343A (en) * | 2020-12-09 | 2021-03-26 | 电子科技大学 | Based on Zn1-xMgxInorganic solar cell with O buffer layer and preparation method thereof |
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