Transparent photocatalyzing thin film, preparation method and semiconductor deviceTechnical field
The present invention relates to technical field of semiconductors, and in particular to a kind of transparent photocatalyzing thin film, preparation method and quasiconductorDevice.
Background technology
Catalysis material is the based semiconductor catalyst material needed for the photochemical reaction for occurring in the presence of light, lightOne important application of catalysis material is exactly automatically cleaning and removes removal organic polluter, and organic pollution includes：Formaldehyde, benzene, volatilizationProperty Organic substance, ammonia, radon etc.；Generally, the specific surface area of catalysis material is bigger and granule is thinner, and catalytic effect is better.However,Grain more thin easier reunion, also results in the appearance of wave particle dualism problem, affects absorption of the catalysis material to light；And granule is tooBig photocatalyst does not have good photolytic activity again, and this has had a strong impact on the automatically cleaning of catalysis material and has removed removal organic polluterEffect.
Content of the invention
In order to overcome problem above, the present invention is intended to provide a kind of transparent photocatalyzing thin film and preparation method thereof so that shouldOn transparent photocatalyzing thin film, vertical-growth goes out very thin continuous nano material film, it is to avoid particle agglomeration and wave particle dualism are askedTopic.
In order to achieve the above object, a kind of transparent photocatalyzing thin film of the present invention, including：One transparent substrates；Vertical-growth inNano net in transparent substrates；The plane of nano net is vertical with transparent substrates；The nano net has multiple micro- engraved structures, andThe bottom of the nano net is mutually bonded by chemical bond with transparent substrates；The material of nano net is conductor photocatalysis material.
Preferably, the nano net is grown perpendicular to transparent substrates by nano wire and the side of adjacent nanowires contacts shapeBecome nano thin-film, then etch to form micro- void region through nano thin-film.
Preferably, mutually it is bonded by chemical bond between the nano wire for contacting.
Preferably, the diameter of nano wire is the thickness of the nano net.
Preferably, the thickness of the nano net is not more than 10nm.
Preferably, the thickness of the nano net is not more than 5 nanometers.
Preferably, the transparent substrates are single-layer graphene film.
Preferably, the catalysis material is wide band gap semiconducter catalysis material.
Preferably, the wide band gap semiconducter catalysis material is the titanium alloy nano line and/or zinc alloy nano-wire.
Preferably, the titanium alloy nano line is titanium dioxide nano thread, and the zinc alloy nano-wire is zinc-oxide nanoLine.
Preferably, micro- engraved structure is nanometer level microporous.
Preferably, the spacing between adjacent described micro- engraved structure is not more than 10nm.
In order to achieve the above object, present invention also offers a kind of preparation side of the transparent photocatalyzing thin film of any of the above-describedMethod, which comprises the following steps：
Step 01：One transparent substrates are provided；
Step 02：Nano thin-film is grown on the transparent substrate；The nano thin-film place plane for being grown is perpendicular to instituteTransparent substrates are stated, the bottom of the nano net is mutually bonded by chemical bond with transparent substrates；
Step 03：Multiple micro- engraved structures are etched on the nano thin-film.
Preferably, in the step 02, the growth course of nano thin-film includes：
Step 021, prepares 1-dimention nano sub-array on the transparent substrate；
Step 022, with nanometer sub-array as base, per nanometer seed is bent to growth nanowire, so as to form nanometerLinear array；
Step 023, the side of adjacent nanowires contacts with each other, so as to form the nano thin-film perpendicular to transparent substrates.
Preferably, in the step 021, the preparation that wherein at least has row of one dimensional nanometer sub-array includes：First,Form nanometer seed precursor solution on the transparent substrate, after drying, form nanometer seed thin film；Secondly, lured using laserWaveguide technology marks nanoscale vestige in the nanometer seed thin film, and nanoscale mark region induces a nanometer sub-array.
Preferably, the live width of the nanoscale vestige is equal to or more than the diameter of nanometer seed, the nanometer sub-arrayThe width of region is equal to the live width of the nanoscale vestige.
Preferably, the live width of the nanoscale vestige is less than 5nm.
Preferably, the live width of the nanoscale vestige is less than 1nm.
Preferably, in the step 021, the preparation that wherein at least has row of one dimensional nanometer sub-array includes：
First, one layer of mask is formed on a transparent substrate；
Then, photoetching is carried out to mask and/or etching forms one nanoscale opening；
Finally, in the exposed transparent substrates of nanoscale opening institute, nanometer sub-array is formed.
Preferably, when the material of mask is photosensitivity material, is etched on mask using photoetching process and receive togetherMeter level opening；When the material of mask is inorganic material, using photoetching and etching technics or only with anisotropic etching workSkill is etching one nanoscale opening on mask.
Preferably, using physical vaporous deposition, sol-gal process, spraying process, galvanoplastic, magnetron sputtering method in nanoscaleNanometer sub-array is formed in the exposed lining transparent substrates of opening institute；Or by seed solution spin coating or drop in nanoscale opening instituteAfter in exposed transparent substrates, drying forms nanometer sub-array.
Preferably, in the step 022, grown using chemical vapour deposition technique, aqua-solution method or electrochemical plating and receiveRice noodle.
Preferably, in the step 03, using plasma lithographic technique or laser-induced thermal etching are etching micro- hollow outStructure.
In order to achieve the above object, present invention also offers a kind of semiconductor device, which includes above-mentioned transparent photocatalyzingThin film.
The transparent photocatalyzing thin film of the present invention, by nano net of the vertical-growth on a transparent substrate in transparent substrates；The plane of nano net is vertical with transparent substrates；The nano net being made up of conductor photocatalysis material has multiple engraved structures, andThe bottom of nano net is mutually bonded by chemical bond with transparent substrates, the three dimensional structure should with transparent substrates and vertical nanowires net,Due to the diameter that the thickness of nano net is nano wire, by controlling diameter and the length of nano wire, you can so that nano net hasTransparent nature, so, the thickness of nano net and/or height are all very small, and the catalysis material granule that can break traditions is lessThe reunion that causes, the problem of wave particle dualism, along with nano net has micro- engraved structure, further increase the ratio of nano netSurface area, improves photocatalysis efficiency, while in this nanometer web frame, when micro- engraved structure accomplishes nanoscale, acceptableThere is higher molecular filtration ability, additionally, this nanometer web frame can also be applied to detection of gas field.
Description of the drawings
Fig. 1 is the overlooking the structure diagram of the transparent photocatalyzing thin film of embodiments of the invention one
Fig. 2 is the cross section structure schematic diagram of the transparent photocatalyzing thin film of embodiments of the invention one
Fig. 3 is the schematic flow sheet of the preparation method of the transparent photocatalyzing thin film of embodiments of the invention two
Fig. 4-6 is each step schematic diagram of the preparation method of the transparent photocatalyzing thin film of embodiments of the invention two
Fig. 7-9 is each step schematic diagram of the nano thin-film growth course of embodiments of the invention two
Figure 10-11 is each step schematic diagram of the preparation process of the one-dimensional nano line array of embodiments of the invention two
Figure 12-14 is each step schematic diagram of the preparation process of the one-dimensional nano line array of embodiments of the invention two
Specific embodiment
For making present disclosure more clear understandable, below in conjunction with Figure of description, present disclosure is made into oneStep explanation.The specific embodiment the invention is not limited in certainly, the general replacement known to those skilled in the artCover within the scope of the present invention.
Embodiment one
Below in conjunction with accompanying drawing 1-2 and specific embodiment, the present invention is described in further detail.It should be noted that, accompanying drawing is equalIn the form of simplify very much, using non-accurately ratio, and only in order to convenient, clearly reach and aid in illustrating the present embodimentPurpose.
Fig. 1 and Fig. 2 is referred to, the transparent photocatalyzing thin film of the present embodiment includes：One transparent substrates 101；Vertical-growth inNano net (shown in dotted line inframe) in transparent substrates 101；In the present embodiment with 101 previous column nano-wire array of transparent substrates it isExample is illustrated, but this is not used in and limits the scope of the invention.The plane of nano net (shown in dotted line inframe) and transparent liningBottom 101 is vertical；Nano net has multiple micro- engraved structures 103, and the bottom of nano net passes through chemical bond phase with transparent substrates 101Bonding；The material of nano net is conductor photocatalysis material.In the present embodiment, the array that micro- engraved structure 103 is staggered in alternatingArrangement, micro- engraved structure 103 may be located at the side wall touching position of the nano wire 102 of nano net, it is also possible to positioned at nano wire 102On.Here nano net is to be grown perpendicular to transparent substrates 101 by nano wire 102 and the side of adjacent nanowires 102 contactsNano thin-film is formed, then etches to form micro- void region 103 through nano thin-film.Meanwhile, pass through between the nano wire 102 for contactingChemical bond is mutually bonded, and can cause on 102 boundary of adjacent nanowires due to contacting during the lateral growth of adjacent nanowires 102A certain degree of continued growth at face, so as between the nano wire 102 that these contact due to the combination that has these chemical bonds andMore firm, so as to constitute a nano thin-film.Here, the diameter of nano wire 102 is the thickness of nano net, can be by controlDiameter when growth technique processed such as time, temperature etc. are to control adjacent nanowires 102 to contact, so as to form desired thicknessNano thin-film；While the height of nano thin-film can also be controlled by controlling growth technique, relatively thin and shorter so as to obtainNano thin-film, to improve specific surface area and the photocatalytic activity of nano thin-film, while nano thin-film can also be avoided blocked up orThe too high transparency for reducing whole transparent photocatalyzing thin film.Preferably, the thickness of nano net is not more than 10nm, for example, 5-7nm.
The transparent substrates 101 of the present embodiment can be single-layer graphene film, conductive or non-conductive flexible transparent substrate, exampleSuch as ito thin film, FTO thin film etc..
In the present embodiment, as nano net needs the light that can realize transparent photocatalyzing thin film with photocatalysis performance to urgeChange ability, therefore, the material of nano net is conductor photocatalysis material.Preferably, catalysis material is broadband gap photocatalytic materialMaterial.Accordingly, nano wire 102 can also be wide band gap semiconducter nano wire, for example, titanium alloy nano line or kirsite nanometerLine, and, the cost of both alloy materials is relatively low, advantageously in large-scale production.Wherein, titanium alloy nano line is permissibleTitanium dioxide nano thread is chosen as, zinc alloy nano-wire can be chosen as zinc oxide nanowire；The crystal formation of titanium dioxide nano threadCan be Ca-Ti ore type or rutile-type, the crystal formation of zinc oxide nanowire is hexahedron structure.
It should be noted that when nanowire sidewalls contact, merge between nanowire sidewalls, for example, if nano wireFor titanic oxide material, then merge between adjacent nano line side wall.
In the present embodiment, micro- engraved structure 103 can be nanometer level microporous, preferably, nanometer level microporous can be not more than10nm, it is preferable that no more than 5nm；Preferably, the spacing between adjacent micro- engraved structure 103 is not more than 10nm.Micro- hollow out knotThe setting of structure 103, not only increases the specific surface area of nano net, also improves the adsorption efficiency of nano net, meanwhile, micro- hollow out knotThe nano net formed by structure 103 from for another kind of angle, equivalent to being that multiple less nanostructureds are constituted in nano net,So as to further increase the photocatalysis effect of nano net.It should be noted that micro- engraved structure of the present invention is not limited to this realityThe nanometer level microporous of example is applied, shape is not limited to circle, can also be other shapes, such as：Regular polygon, irregular figure etc. are equalCan, the invention is not limited in this regard.
Additionally, nano net can be also used for filtration, detection of gas.When micro- engraved structure 103 is for nanometer level microporous, particularlyWhen spacing between adjacent micro- engraved structure 103 is not more than 10nm, the filtration of bigger molecule is can be also used for.
Embodiment two
Below in conjunction with accompanying drawing 3-14 and specific embodiment, the present invention is described in further detail.It should be noted that, accompanying drawingAll in the form of simplify very much, using non-accurately ratio, and only in order to convenient, clearly reach aid illustration the present embodimentPurpose.
Fig. 3 is referred to, is illustrated by taking transparent substrates previous column nano-wire array as an example in the present embodiment, but this is not used inLimit the scope of the invention.In the present embodiment, the preparation method of the transparent photocatalyzing thin film of above-described embodiment one includes：
Step 01：Fig. 4 is referred to, transparent substrates 101 are provided；
Step 02：Fig. 5 is referred to, growth nano thin-film (shown in dotted line inframe) in transparent substrates 101；Grown receivesRice thin film place plane is perpendicular to transparent substrates 101, and the bottom of nano net is mutually bonded by chemical bond with transparent substrates 101；ChangeIt is being bonded between atom and the atom of the material composition of transparent substrates 101 in nano net material composition, for example, nanometer to learn keyNet materials are titanium dioxide, the material of transparent substrates 101 be Graphene, then the titanium atom of titanium dioxide and/or or oxygen atom withThe carbon atom of Graphene is mutually bonded and obtains Ti-C key and/or C-O key.
Step 03：Fig. 6 is referred to, on nano thin-film (shown in dotted line inframe), etches multiple micro- engraved structures 103.ThisIn, micro- engraved structure 103 can be etched with using plasma lithographic technique or laser-induced thermal etching.
Specifically, in 02 the step of the present embodiment, the growth course of nano thin-film can include：
Step 021, refers to Fig. 7, prepares 1-dimention nano sub-array 201 in transparent substrates 101；For example, metatitanic acid kindSub- solution or zinc acetate seed solution, this is that those skilled in the art could be aware that, repeats no more here.
Step 022, refers to Fig. 8, and with nanometer sub-array 201 as base, per nanometer seed is bent to growth nanowire202, so as to form nano-wire array；Here it is possible to using chemical vapour deposition technique, aqua-solution method or electrochemical plating next lifeLong nano wire 202.For example, titanium dioxide nano thread is prepared using hydro-thermal method, and solution concentration is placed in for 0.04M precursor solutionIn reactor, at a temperature of 100～150 DEG C, constant temperature grows 01～0.5 hour, diameter is finally obtained less than the two of 10nmTitanium oxide nano wire.Again for example, zinc oxide nanowire is prepared using hydro-thermal method, and solution concentration is put for 0.05M precursor solutionIn reactor, at a temperature of 90～140 DEG C, constant temperature grows 01～0.5 hour, and oxygen of the diameter less than 10nm is finally obtainedChange zinc nano wire.Preparation with regard to nano wire is also the ordinary skill in the art, is that those skilled in the art could be aware that, thisIn repeat no more.
Step 023, refers to Fig. 9, and the side of adjacent nanowires contacts with each other, so as to form receiving perpendicular to transparent substratesRice thin film.The diameter of the nano wire 203 in step 023 is all higher than the diameter of the nano wire 202 in step 022, in step 023The length of nano wire 203 is all higher than the length of the nano wire 202 in step 022, and for example, it is constant to be further continued for above-mentioned growth conditionss,Extend growth time 0.1～0.5 hour so that nano wire cross growth is contacted, the nano titania so as to form required is thinFilm or zinc oxide nano film.The growth technique of nano wire can adopt conventional method, for example, it is possible to by other conditions notBecome, extend growth time, or the longitudinal growth of nano wire is realized by the different growth temperature of two steps or precursor concentrationAnd cross growth.
Require emphasis, the mode of the nano thin-film perpendicular to transparent substrates growth of the present embodiment, change traditionalThe parallel mode being formed on substrate of nano thin-film, having broken nano thin-film can only be parallel to the idea of substrate.This perpendicular toThe structure of the nano thin-film of substrate, will more be applied in semiconductor applications.
Here, realize the controlled of nanowire diameter when nanowire sidewalls contact with each other and can take following manner：
It is possible, firstly, to by substantial amounts of experiment obtain other conditions constant when, under precursor solution concentration permanence conditionNano wire longitudinal direction average growth rate and horizontal average growth rate；And when other conditions are constant, dense in precursor solutionDegree is different as nano wire longitudinal direction average growth rate and horizontal average growth rate under conditions of concentration M1 or M2；In the same manner, also may be usedTo obtain different temperatures P1 or the longitudinal direction average growth rate of the nano wire under the conditions of P2 and horizontal average growth rate.
Then, the target of nano wire, according to the average growth rate that is tried to achieve, under the conditions of corresponding growing environment, is setDiameter D and target length L；
Then, the position of nano wire, according to aimed dia D, is set on a transparent substrate, and the position of nano wire that is to say kindThe position of son；The theoretical pitch of seed is also D, in actual process, it may appear that multiple seeds assemble situations, as long as the model in DThere is at least one seed, so, if form one-dimensional continuous nanometer seed membrane can achieve in enclosing；Furthermore, it is also possible toCombined using template and etching technics, the preparation of specific 1-dimention nano sub-array will be in subsequent detailed description.
Then, the calculating with regard to the growth time and diameter of step 22 and step 23 can adopt following process：
A kind of method is：T1 the time required to obtaining average for D/ longitudinal growth speed is set, by L/ average transverse growth speedRate obtain the time required to t2, it is contemplated that required nanowire diameter is the principal element for determining nanometer thickness of net, no matter t1 and t2Size how, and selected actual growth time t should be greater than or be equal to time t1；In the premise that nanowire growth environment is constantUnder, substantial step 022 and step 023 are continuous processes, and the total growth time that need to only arrange nano wire is t.
Another kind of method is：Can when other conditions are constant, according to precursor solution concentration difference under conditions of receiveRice noodle longitudinal direction average growth rate and horizontal average growth rate, using the aimed dia D for setting nano wire and target length L,Select the precursor concentration for step 022 and step 023 respectively, and calculate corresponding growth time, now, step 022The concentration of precursor solution is set to M1, and growth time is set to T1；The concentration of the precursor solution of step 023 is set to M2, then basisNano wire longitudinal direction average growth rate V1 (being obtained by many experiments before) under concentration M1, obtains step 022 completeBecome the diameter D1=V1*T1 of rear nano wire；Again by aimed dia D-D1, difference in diameter D2 is obtained, then, according under concentration M2Nano wire longitudinal direction average growth rate V2 (being obtained by many experiments before), when obtaining the growth needed for step 023Between T2=D2/V2.In this case, preferably, selected precursor solution concentration M1 ＜ M2 so that the horizontal life of step 023Long-time shortens.
Yet another method is：Can be indulged according to nano wire under conditions of growth temperature difference when other conditions are constantTo average growth rate and horizontal average growth rate, using the aimed dia D for setting nano wire and target length L, select respectivelyThe precursor concentration for step 022 and step 023 is selected, and corresponding growth time is calculated, now, the growth temperature of step 022Degree is set to P1, and growth time is set to T1；The growth temperature of step 023 is set to P2, then according to the nano wire under growth temperature P1Longitudinal average growth rate V1 (being obtained by many experiments before), obtains the diameter D1 of nano wire after the completion of step 022=V1*T1；Again by aimed dia D-D1, difference in diameter D2 is obtained, then, longitudinally flat according to the nano wire under growth temperature P2All growth rate V2 (being obtained by many experiments before), obtains the growth time T2=D2/V2 needed for step 023.ShouldIn the case of, preferably, selected growth temperature P1 ＜ P2 so that the cross growth time of step 023 shortens.
It should be noted that the concrete technology of the preparation, the longitudinal growth of nano wire and cross growth with regard to Seed Layer is equalIt is that those skilled in the art could be aware that.
The preparation process of wherein row of one dimensional nanometer sub-array is described below in detail.
In the present embodiment, the preparation that wherein at least has row of one dimensional nanometer sub-array can include：
First, Figure 10 is referred to, forms nanometer seed precursor solution on a transparent substrate, after drying, form nanometer seedThin film 301；Here, various nanometer seed presomas are different because of the difference of nano material, for example, before zinc-oxide nano seedIt can be zinc acetate solution to drive liquid solution, and the precursor solution of nano titania seed can be titanium chloride solution etc., thisIt is that those skilled in the art could be aware that, repeats no more here.
Secondly, refer to Figure 11, nanoscale vestige marked in nanometer seed thin film 301 using induced with laser technology, is receivedMeter level mark region (in Figure 11 shown in dotted line frame) induces nanometer sub-array 302.Here, the live width of nanoscale vestige is permissibleEqual to or more than the diameter of nanometer seed, the width of 302 region of nanometer sub-array is equal to the live width of nanoscale vestige.RelativelyGood, the live width of nanoscale vestige is less than 5nm, and further, the live width of nanoscale vestige less for example can be less than1nm, so that the diameter of the nanometer seed for growing is less than 5nm or even 1nm, and the nano wire that goes out of subsequent growth is straightFootpath is unlikely to excessive, or even in below 5nm.It should be noted that as the nanoscale vestige of induced with laser is continuous and lineWide ultra-fine so that the seed spacing in nanometer sub-array and the live width of seed diameter respectively less than nanoscale vestige.
Additionally, in the present embodiment, the preparation that wherein at least has row of one dimensional nanometer sub-array can also adopt following stepSuddenly：
First, Figure 12 is referred to, forms one layer of mask 401 on a transparent substrate；
Then, Figure 13 is referred to, and photoetching is carried out to mask 401 and/or etching forms one nanoscale opening 402；Here,When the material of mask 401 is photosensitivity material, one nanoscale can be etched on mask 401 using photoetching process and openMouth 402；When the material of mask 401 is inorganic material, photoetching and etching technics can be adopted or carved only with anisotropyEtching technique is etching one nanoscale opening 402 on mask 401.With regard to the formation of the nanoscale opening 402, using existingPhotoetching process can accomplish 10nm, 7nm 7nm, 5nm, 3nm technology included below using be repeated several times exposure and extreme ultravioletPhotoetching (EUV) technology can be achieved on.Therefore, the nanoscale opening 402 of the present embodiment can accomplish the live width of below 10nm,Nanometer the diameter of seed and the diameter of spacing and the nano wire for being formed be also atomic little, the nano thin-film of the present embodiment andNano net is expected to large-scale production and applies.
Finally, Figure 14 is referred to, and Figure 13 is combined, in the exposed transparent substrates of 402 institute of nanoscale opening, form nanometerSub-array 403.Here it is possible to be existed using physical vaporous deposition, sol-gal process, spraying process, galvanoplastic, magnetron sputtering methodNanometer sub-array 403 is formed in the exposed transparent substrates of nanoscale opening institute；Or by seed solution spin coating or drop in nanometerDrying after in the 402 exposed transparent substrates of institute of level opening forms nanometer sub-array 403.Shape with regard to nanometer sub-array 403Become and can adopt common process, for different nano materials using different nano materials precursor solution preparing,Usually spin-coating method, instillation are formed at nanometer seed precursor solution in nanoscale opening, through noble gases such as nitrogenDry up, nanometer seed precursor film is formed, nanometer seed forerunner can be caused through such as not higher than 100 DEG C of temperature of low-temperature heatA nanometer sub-array is crystallized out on body film, and this is also that those skilled in the art could be aware that, repeats no more here.Due to nanometerThe live width of level opening 402 is superfine so that the diameter of nanometer seed and spacing are all less, so that the nano wire for being formed is straightThe thickness in footpath, the thickness of nano thin-film and nano net is all in nanoscale for example in below 10nm, minimum so as to obtain sizeNano net, with higher specific surface area, further suppress existing superfine nanoparticle agglomerates and wave particle dualism problem,Therefore, the transparent photocatalyzing thin film of the present embodiment has higher photocatalysis efficiency and good transparency, can apply to instituteThe field of transparent material in need, such as window, screen, on clear glass, these transparent materials can be used as transparent certainlyThe transparent substrates of photocatalysis film, not only can printing opacity, being also used as molecular sieve carries out the filtration of molecular level, sterilization, eliminatesHarmful gass, can also carry out detection of gas and be applied in gas sensor, and be applied to medical treatment, biological field etc..
Although the present invention with preferred embodiment disclose as above, so the embodiment illustrate only for the purposes of explanation and, the present invention is not limited to, if those skilled in the art can make without departing from the spirit and scope of the present inventionDry change and retouching, the protection domain advocated by the present invention should be to be defined described in claims.