CN104698512A - Member with reflection preventing function and manufacturing method thereof - Google Patents
Member with reflection preventing function and manufacturing method thereof Download PDFInfo
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- CN104698512A CN104698512A CN201410743609.8A CN201410743609A CN104698512A CN 104698512 A CN104698512 A CN 104698512A CN 201410743609 A CN201410743609 A CN 201410743609A CN 104698512 A CN104698512 A CN 104698512A
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- base material
- pellumina
- reflective function
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
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- Optics & Photonics (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Optical Filters (AREA)
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Abstract
The invention provides a member with a reflection preventing function and a manufacturing method thereof. A thin alumina film is uniformly formed on a substrate, and a uniform micro concave-convex reflection preventing structure is obtained. The member (10) with a reflection preventing function is provided with a substrate (11) and a reflection preventing film (13) on the surface of the substrate (11). The reflection preventing film (13) performs hydro-thermal treatment on the alumina film by using high-temperature water or steam, the alumina film being formed by an atomic layer deposition method, and thus, the micro concave-convex structure is formed.
Description
Technical field
The present invention relates to the parts and manufacture method thereof with anti-reflective function.
Background technology
Lens, flat pannel display (FPD) substrate, semiconductor substrate etc. require anti-reflection structure.As anti-reflection structure, there will be a known by forming fine concaveconvex structure on the surface of base material and make not produce so-called moth eye (moth eye) structure of violent variations in refractive index.Form minute concave-convex structure on surface as this and form the method for anti-reflection structure, propose to form pellumina etc. on base material after, carry out the hydrothermal treatment consists (such as patent documentation 1,2) that impregnated in the hot water of below boiling point.
As the formation method of pellumina in this case, disclose sol-gel process at patent documentation 1, disclose chemical vapor deposition method (CVD), physical vapor deposition (PVD method) at patent documentation 2.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-72046 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-198330 publication
Summary of the invention
The technical matters solved is wanted in invention
But, as optics except anti-reflective function, also need high light transmission function, namely, do not damage through the function of transmissivity of light, the thickness of the pellumina formed is thicker, transmissivity more can reduce because of the absorption of light, therefore, needing to make pellumina is as far as possible film (below 100nm).But, when the large substrate that FPD substrate is such, in sol-gel process, CVD, PVD method, be difficult to the film being formed uniformly below 100nm.
On the other hand, when the large base material of refractive index such as silicon wafer forms the such anti-reflection structure recorded in patent documentation 1,2, the refractive index of aluminium oxide is 1.6, and the refractive index of silicon is 3.8, their refringence is large, also can produce and be difficult to the sufficient situation of anti-reflection effect.
The present invention completes in light of this situation, and its problem is that providing a kind of can be formed uniformly parts that thin pellumina obtains the anti-reflection structure of uniform micro concavo-convex shape, that have anti-reflective function and manufacture method thereof on base material.
In addition, its problem is that the base material providing refractive index large also can obtain the parts with anti-reflective function and the manufacture method thereof of sufficient anti-reflective function.
For solving the technical scheme of problem
In order to solve above-mentioned problem, a first aspect of the present invention provides a kind of parts with anti-reflective function, it is characterized in that, comprise: base material and be formed in the antireflection film on surface of above-mentioned base material, above-mentioned antireflection film carries out hydrothermal treatment consists by utilizing the hot water of high temperature or water vapor to the pellumina formed by atomic layer deposition method, is formed with minute concave-convex structure thus.
In above-mentioned first aspect, the above-mentioned parts with anti-reflective function can be used as optics or device formation is used or the substrate of flat-panel monitor.In addition, above-mentioned pellumina can be formed by alternative supply trimethyl aluminium and oxygenant.
A second aspect of the present invention provides a kind of manufacture method with the parts of anti-reflective function, it is characterized in that, comprising: the operation being formed pellumina by atomic layer deposition method on the surface of base material; Form minute concave-convex structure with utilizing the hot water of high temperature or water vapor to implement hydrothermal treatment consists to above-mentioned pellumina, make the operation of antireflection film.
In above-mentioned second aspect, above-mentioned pellumina can be formed by alternative supply trimethyl aluminium and oxygenant.
A third aspect of the present invention provides a kind of parts with anti-reflective function, it is characterized in that, the fine uneven portion with anti-reflective function is formed on the surface of base material, above-mentioned fine uneven portion is formed as follows: form pellumina on the surface of above-mentioned base material, then, hydrothermal treatment consists is carried out to pellumina and forms micro concavo-convex shape aluminium oxide, then, with above-mentioned micro concavo-convex shape aluminium oxide for etching mask carries out dry ecthing to the surface of above-mentioned base material, and by above-mentioned micro concavo-convex shape aluminium oxide removing.
In the above-mentioned third aspect, the pellumina preferably used when forming above-mentioned fine uneven portion is formed by atomic layer deposition method.In addition, the parts with anti-reflective function can be used as the substrate of optics or device formation use or flat-panel monitor.
A fourth aspect of the present invention provides a kind of manufacture method with the parts of anti-reflective function, it is characterized in that, comprising: the operation forming pellumina on the surface of base material; Utilize the hot water of high temperature or water vapor to implement hydrothermal treatment consists to above-mentioned pellumina, form the operation of micro concavo-convex shape aluminium oxide; With with above-mentioned micro concavo-convex shape aluminium oxide for etching mask carries out dry ecthing to the surface of above-mentioned base material, form fine uneven portion on the surface of above-mentioned base material, and, by the removing of above-mentioned micro concavo-convex shape aluminium oxide, form the operation of anti-reflection structure.
In above-mentioned fourth aspect, the operation being preferably formed above-mentioned pellumina is undertaken by atomic layer deposition method.
A fifth aspect of the present invention provides a kind of parts with anti-reflective function, it is formed with the fine uneven portion with anti-reflective function on the surface of base material, the above-mentioned feature with the parts of anti-reflective function is: above-mentioned fine uneven portion is formed as follows: form the refractive index near the refractive index with substrate on the surface of above-mentioned base material, etched easy etching film easier than base material, pellumina is formed on the surface of above-mentioned easy etching film, then, hydrothermal treatment consists is carried out to pellumina and forms micro concavo-convex shape aluminium oxide, then, with above-mentioned micro concavo-convex shape aluminium oxide for dry ecthing is carried out on the surface of etching mask to above-mentioned easy etching film, and, by above-mentioned micro concavo-convex shape aluminium oxide removing.
A sixth aspect of the present invention provides a kind of manufacture method with the parts of anti-reflective function, it is characterized in that, comprising: the operation forming the refractive index near the refractive index with substrate, etched easy etching film easier than base material on the surface of base material; The operation of pellumina is formed on the surface of above-mentioned easy etching film; The hot water of high temperature or water vapor is utilized to implement to above-mentioned pellumina the operation that hydrothermal treatment consists forms micro concavo-convex shape aluminium oxide; With with above-mentioned micro concavo-convex shape aluminium oxide for dry ecthing is carried out on the surface of etching mask to above-mentioned easy etching film, form fine uneven portion on the surface of above-mentioned easy etching film, and, by the removing of above-mentioned micro concavo-convex shape aluminium oxide, form the operation of anti-reflection structure.
In in the above-mentioned 5th and the 6th, the pellumina used when being preferably formed above-mentioned fine uneven portion is formed by atomic layer deposition method.In addition, in the above-mentioned 5th and the 6th, be applicable to when above-mentioned base material is the such difficult etching substrate of glass substrate, nesa coating or color filter.
Invention effect
According to the first and second aspects of the present invention, for base material, after its surface forms pellumina, carry out hydrothermal treatment consists and form minute concave-convex structure, when forming antireflection film thus, atomic layer deposition method is utilized to form pellumina, therefore, even if when large substrate, also thin pellumina can be formed uniformly in base material entirety, high light transmission function can not be damaged, be formed uniformly the antireflection film in micro concavo-convex shape at the surface integral of base material.
According to the third and fourth aspect of the present invention, micro concavo-convex shape aluminium oxide that hydrothermal treatment consists formed is carried out after pellumina for etching mask to be formed on the surface of base material, dry ecthing is implemented to substrate surface, fine uneven portion is formed at substrate surface, and, the removing of micro concavo-convex shape aluminium oxide is formed anti-reflection structure, therefore, even if be the base material that refractive index is large, also can not produce the reflection caused by refringence, obtain sufficient anti-reflective function.
According to the of the present invention 5th and the 6th aspect, refractive index near the refractive index with substrate is formed and than base material after easier etched easy etching film on the surface of base material, to carry out micro concavo-convex shape aluminium oxide that hydrothermal treatment consists formed after pellumina for etching mask being formed, dry ecthing is implemented on commute etching film surface, fine uneven portion is formed at substrate surface, and, the removing of micro concavo-convex shape aluminium oxide is formed anti-reflection structure, therefore, even if be the large and base material of difficult etching of refractive index, also the reflection caused by refringence can not be produced, obtain sufficient anti-reflective function.
Accompanying drawing explanation
Fig. 1 is the sectional view with the parts of anti-reflective function representing that the first embodiment of the present invention relates to.
Fig. 2 is the figure with the formation method of the antireflection film of the parts of anti-reflective function related to for illustration of the first embodiment of the present invention.
Fig. 3 is the sectional view with the parts of anti-reflective function representing that the second embodiment of the present invention relates to.
Fig. 4 is the figure with the formation method of the fine uneven portion of the parts of anti-reflective function related to for illustration of the second embodiment of the present invention.
Fig. 5 be for illustration of with substrate surface formed Al
2o
3film, the film carrying out the micro concavo-convex shape that hydrothermal treatment consists is formed are the figure of the variations in refractive index of surface portion in antireflection film situation.
Fig. 6 is the figure of variations in refractive index of surface portion when forming fine uneven portion for illustration of the substrate surface in the second embodiment of the present invention.
Fig. 7 is the sectional view with the parts of anti-reflective function representing that the 3rd embodiment of the present invention relates to.
Fig. 8 is the figure with the formation method of the fine uneven portion of the parts of anti-reflective function related to for illustration of the 3rd embodiment of the present invention.
Fig. 9 be for illustration of with formed at substrate surface easy etching film so that its surface formed Al
2o
3after film, the figure of the variations in refractive index of the film that carries out the micro concavo-convex shape that hydrothermal treatment consists is formed surface portion when being antireflection film.
Figure 10 is the figure of the variations in refractive index of surface portion when forming fine uneven portion for illustration of the easy etching film surface in the 3rd embodiment of the present invention.
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are described.
< first embodiment >
Fig. 1 is the sectional view with the parts of anti-reflective function representing that the first embodiment of the present invention relates to.
The parts 10 with anti-reflective function of the present embodiment have base material 11, also have the antireflection film 13 of that be formed in the surface of base material 11, in micro concavo-convex shape moth ocular structure.Himself can be used as the opticses such as lens by parts 10, also can be used as the substrate that device forms use and FPD.
The material of base material 11 is not particularly limited, can be any number of in glass, semiconductor, pottery, plastics, metal, silicon can being illustrated when using as device substrate as typical case, glass can be illustrated as typical case when using as the substrate of FPD and lens.
Antireflection film 13 forms aluminium oxide (Al utilizing atomic layer deposition method (ALD method)
2o
3) after film, carry out hydrothermal treatment consists and make Al
2o
3film is concavo-convex.
Referring to Fig. 2, the formation method of antireflection film 13 is specifically described.
As shown in Fig. 2 (a), ALD method is utilized to form Al at first on the surface of base material 11
2o
3film 14.
Al is formed utilizing ALD method
2o
3during film 14, formed by Al containing Al gas and oxygenant by repeatedly repeatedly supplying successively
2o
3the operation of the thin unit membrane formed, namely contains Al gas and oxygenant by alternative supply, forms the Al of the thickness of regulation
2o
3film.Specifically, base material is received in container handling, by base material heating to set point of temperature, and, the vacuum tightness of regulation will be vented in container handling, in this condition, by " cleaning containing in the supply → container handling of the cleaning → oxygenant in the supply → container handling of Al gas " as a circulation for the formation of unit membrane, multiple circulation repeatedly.
Be not particularly limited containing Al gas, be normally used material, such as, can illustrate trimethyl aluminium (TMA): Al (CH
3)
3.Such as H can be used as oxygenant
2o, O
3, O
2plasma.
Al now
2o
3the thickness of film 14 preferably can utilize hydrothermal treatment consists to obtain the thickness of desired anti-reflection structure.From this point, preferred below 100nm, more preferably 10 ~ 50nm.
Then, as shown in Fig. 2 (b), to Al
2o
3film 14 implements hydrothermal treatment consists, at Al
2o
3film 14 is formed has fine protuberance 15 and the micro concavo-convex of recess 16.Thus, the antireflection film 13 of micro concavo-convex shape is formed.
Hydrothermal treatment consists can be undertaken by method disclosed in above-mentioned patent documentation 1 and 2.Specifically, the method etc. that can utilize the method for the alkaline aqueous solution that impregnated in hot water or high temperature or be exposed to water vapor is carried out.Thus, formed than original Al
2o
3dark concavo-convex of the thickness of film 14.Now, preferably whole Al is not made
2o
3film 14 reacts in the hot water, and remains Al with unreacted state
2o
3the lower layer side of film 14.This is because, carry out reacting and the part of micro concavo-convex shape reduces with the adaptation of base material 11, become easy stripping, but by the Al of remained unreacted
2o
3the cause that film can suppress adaptation to reduce.Unreacted Al
2o
3the thickness of film is preferably 1 ~ 25nm.The alkaline aqueous solution of hot water or high temperature is preferably more than 60 DEG C and below boiling temperature.Dip time wherein, by Al
2o
3the thickness of film is determined, is preferably 1 second ~ about 30 minutes, is more preferably 10 seconds ~ 10 minutes.Processing time when being exposed to the method for water vapor is preferably 1 minute ~ 24 hours.
The fine protuberance 15 formed by this hydrothermal treatment consists and recess 16 such as can be formed with the pitch of about 100nm, can be set to according to the short pitch of the wavelength of the light penetrated, the shape of micro concavo-convex is needle-like or fusiform, therefore, refractive index consecutive variations in the depth direction, can obtain anti-reflective function.
Be formed in the degree of depth (height of protuberance) of the micro concavo-convex of antireflection film 13 in order to good anti-reflective function can be obtained, be preferably 100 ~ 500nm.
Antireflection film 13 has good antireflection, when being especially in use in light transparent member, needing to be formed as not making transmissivity unnecessarily worsen (absorption of light), does not make adaptation reduce, therefore, and Al
2o
3the condition that the thickness demand fulfillment of film is above-mentioned.That is, in order to meet transmissivity, needing film forming in the scope of below 100nm, more preferably 25 ~ 50nm, in order to improve adaptation, needing the Al of remained unreacted
2o
3film 1 ~ 25nm.But, when large-area substrate, must in face equably (preferably ± less than 5%) form this thin film, in addition, unreacted Al
2o
3film is the such very thin thickness of 1 ~ 25nm, therefore, in order to control it accurately, still needs the Al becoming substrate
2o
3the homogeneity of film is very high.But, by the CVD, the PVD method that propose all the time, thickness thin like this can not be formed uniformly.
To this, in the present embodiment, ALD method is used to form Al
2o
3film 14, so, Al can be formed with thin uniform film thickness
2o
3film 14.In addition, the Step Coverage (stepcoverage) of ALD method is good, therefore, substrate exists works, also can be formed uniformly Al in the entirety of base material 11
2o
3film 14.Namely, in ALD method, the operation of the unit membrane that repeated multiple times formation is thin, therefore, can be thin and equably to base material film forming with high Step Coverage, can base material 11 surface integral thin and equably, adaptation forms antireflection film 13 in micro concavo-convex shape well.
In addition, ALD method covers very good as mentioned above, so, not only at the upper surface of base material, and can not the fully back side of the base material of film forming and side film forming in other method.
< second embodiment >
Fig. 3 is the sectional view with the parts of anti-reflective function representing that the second embodiment of the present invention relates to.
The parts 20 with anti-reflective function of the present embodiment are formed with the fine uneven portion 22 of the moth ocular structure with anti-reflective function on the surface of base material 21.Himself can be used as the opticses such as lens by parts 20, also can be used as the substrate that device forms use and FPD.
The material of base material 21 is not particularly limited, can be any number of in glass, semiconductor, pottery, plastics, metal, silicon can being illustrated when using as device substrate as typical case, glass can be illustrated as typical case when using as the substrate of FPD and lens.
Fine uneven portion 22 can be formed as follows: form Al on base material 21 surface
2o
3film, then carries out hydrothermal treatment consists and makes Al
2o
3film is micro concavo-convex shape Al
2o
3, use this micro concavo-convex shape Al
2o
3as etching mask, dry ecthing is carried out to the surface of base material 21, this micro concavo-convex of transfer printing, and, by micro concavo-convex shape Al
2o
3removing.
Below, be specifically described with reference to the formation method of Fig. 4 to fine uneven portion 22.As shown in Fig. 4 (a), form Al on base material 21 surface at first
2o
3film 23.In present embodiment, different from the first embodiment, Al
2o
3the formation method of film 23 is not limited to ALD method, such as, also can use other the method such as CVD, PVD method (sputtering method, vacuum vapour deposition).Wherein, from thin and be formed uniformly Al with good base material 21 surface that covers
2o
3the viewpoint of film 23 is set out, same with the first embodiment, preferably uses ALD method.
Al now
2o
3the thickness of film 23 preferably can utilize ensuing hydrothermal treatment consists be formed into the micro concavo-convex of etching mask and can form the thickness of desired fine uneven portion 22.From such a viewpoint, Al
2o
3the thickness preferably 3 ~ 50nm of film 23.
Then, as shown in Fig. 4 (b), to Al
2o
3film 23 implements hydrothermal treatment consists, forms micro concavo-convex shape Al
2o
324.Hydrothermal conditions now can carry out equally with the first embodiment.Micro concavo-convex shape Al
2o
324 are formed as needle-like, fusiform.
Micro concavo-convex shape Al
2o
3the concavo-convex degree of depth (height of protuberance) of 24 can according to suitably settings such as the degree of depth of the fine uneven portion 22 wanting to obtain, preferably 10 ~ 300nm.
Be connected on, as shown in Fig. 4 (c), with micro concavo-convex shape Al
2o
324 start the dry ecthing on base material 21 surface for etching mask.Then, as shown in Fig. 4 (d), to micro concavo-convex shape Al
2o
324 etch together, form the fine uneven portion 22 of the desired degree of depth.According to the degree of depth of fine uneven portion 22, can to micro concavo-convex shape Al
2o
324 etch in addition.
General plasma etching can be used as dry ecthing.As etching gas, can to base material 21 and micro concavo-convex shape Al
2o
3two sides of 24 carry out etching, and suitably can select according to the kind of base material 21.Such as, when base material 21 is silicon, BCl can be illustrated
3, Cl
2, when base material 21 is glass, can BCl be illustrated
3, CF
4, O
2.
The degree of depth (height of protuberance) of fine uneven portion 22 can according to the treatment conditions of etching period, etching gas (kind, flow), condition of plasma (pressure, RF power), treatment temperature etc., micro concavo-convex shape Al as etching mask
2o
324 highly regulate.The degree of depth (height of protuberance) of fine uneven portion 22 suitably can set according to the anti-reflective function wanting to obtain, but preferred 100 ~ 1000nm.
That records with such as above-mentioned patent documentation 1,2 forms Al at substrate surface
2o
3when film, the film carrying out the micro concavo-convex shape that hydrothermal treatment consists is formed are antireflection film, when base material is made up of the material that the refractive index that silicon is such is large, by Al
2o
3the antireflection film formed and the refringence of base material become large, produce reflection at its interface.
Specifically, as shown in Figure 5, formed by Al on the surface of silicon wafer
2o
3when the antireflection film of micro concavo-convex shape formed, before arrival base material, refractive index n is from the n=1 consecutive variations of air to Al
2o
3n=1.6, therefore, it is possible to prevent reflection, but form the silicon n=3.8 of base material, so refringence is large, the anti-reflection effect at the interface of antireflection film and base material is also insufficient.Bad in order to what eliminate that this refringence causes, although above-mentioned patent documentation 2 describes the pH effect film being formed between base material and antireflection film and have the refractive index of the centre of these refractive indexes, but it is cumbersome to form pH effect film, in addition, the refringence between pH effect film and antireflection film or base material can not be eliminated.
To this, in the present embodiment, with the micro concavo-convex shape Al utilizing hydrothermal treatment consists to be formed
2o
3for etching mask carries out dry ecthing to base material, thus as shown in Figure 6, replicated fine relief pattern on base material, so, as shown in Figure 6, can from the refractive index of refractive index n=1 consecutive variations to base material, the refractive index n=3.8 of such as silicon of air.Therefore, even if be the base material that refractive index is high, also can not produce the reflection because refringence causes, sufficient anti-reflection effect can be obtained.
In addition, as the method directly forming fine uneven portion at base material, there is the method using pearl (beads) or use electron beam at present, but these methods are when wanting to form micro concavo-convex at large-scale base material, need the longer time.And in the present embodiment, form Al at base material
2o
3carry out hydrothermal treatment consists after film and form micro concavo-convex shape Al
2o
3, carry out dry ecthing using it as etching mask, therefore, even if base material is large-scale, also can forms fine uneven portion in the lump in whole face, can be formed at short notice.
< the 3rd embodiment >
Fig. 7 is the sectional view with the parts of anti-reflective function representing that the 3rd embodiment of the present invention relates to.
The parts 30 with anti-reflective function of the present embodiment be formed on the surface of base material 31 there is base material 31 refractive index near (preferred index difference is less than 0.1) refractive index, compared with base material 31 easy etched easy etching film 32, be formed with the fine uneven portion 33 of the moth ocular structure with anti-reflective function on the surface of easy etching film 32.
This structure is at such as base material 31 difficult etching material, such as glass substrate, nesa coating, color filter etc., and it is effective for being difficult to when directly forming fine uneven portion.
That is, as the second embodiment, at base material and Al
2o
3when there is larger refringence in film, the micro concavo-convex shape Al formed to utilize hydrothermal treatment consists
2o
3for etching mask carries out dry ecthing to base material, to form micro concavo-convex pattern be effective, but be difficult to be suitable for when the difficult etching material of base material.
Therefore, in the present embodiment, formed on base material 31 by refractive index and base material 31 close to and etch the easy etching film 32 that easy material forms, this easy etching film 32 is implemented to the micro concavo-convex shape Al utilizing hydrothermal treatment consists to be formed
2o
3for the etching of etching mask, form the fine uneven portion 33 with the moth ocular structure of anti-reflective function on the surface of easy etching film 32.
Specifically, operate as shown in Figure 8, form the parts 30 with anti-reflective function.That is, as shown in Fig. 8 (a), on difficult etching base material 31, form easy etching film 32 with suitable film forming method at first, then, as shown in Fig. 8 (b), form Al on easy etching film 32 surface
2o
3film 34.Al now
2o
3the formation method of film 34, with the Al of the second embodiment
2o
3film 23 is same, is not limited to ALD method, such as, can uses other method of CVD, PVD method (sputtering method, vacuum vapour deposition) etc., but preferably uses ALD method.In addition, Al
2o
3the thickness of film 34 etc. also with the Al of the second embodiment
2o
3film 23 is same.Then, as shown in Fig. 8 (c), to Al
2o
3film 34 implements hydrothermal treatment consists, forms micro concavo-convex shape Al
2o
335.Hydrothermal conditions now can carry out equally with the first embodiment, micro concavo-convex shape Al
2o
335 are formed as needle-like, fusiform.Then, as shown in Fig. 8 (d), with micro concavo-convex shape Al
2o
335 is etching mask, starts the dry ecthing on easy etching film 32 surface.Then, as shown in Fig. 8 (e), commute etching film 32 and micro concavo-convex shape Al
2o
335 etch, and form the fine uneven portion 33 of the desired degree of depth.
The degree of depth preferably 100 ~ 1000nm of fine uneven portion 33.In addition, preferred non commuting etching film 32 all etches, and remains the lower layer side of easy etching film 32 with non-etching state.This is the adaptation in order to ensure fine uneven portion 33 and base material 31.
When present embodiment, need to form easy etching film 32 in centre, therefore, more bother compared with the second embodiment, suitably select the material of easy etching film 32 according to base material 31, substantially can eliminate the refringence of base material 31 and easy etching film 32, same with the second embodiment, do not produce the reflection caused by refringence, sufficient anti-radiation effect can be obtained.
Specifically, as shown in Figure 9, exist by Al on the surface of the large base material (refractive index n=A) of refractive index
2o
3when the fine uneven portion that (refractive index n=1.6) is formed, at Al
2o
3insufficient with the anti-reflection effect at the interface of base material, but at base material and Al
2o
3between the easy etching film (refractive index n=A ± α) that has close to the refractive index of base material (refractive index n=A) is set, the micro concavo-convex shape Al formed to utilize hydrothermal treatment consists
2o
3for etching mask commute etching film carries out dry ecthing, as shown in Figure 10, micro concavo-convex pattern is transferred to easy etching film, thus, the fine uneven portion be made up of the material that refractive index is close is formed on base material, therefore, it is possible to from the refractive index of air roughly consecutive variations to the refractive index of base material.
Other application of < >
In addition, the invention is not restricted to above-mentioned embodiment, can various distortion be carried out.Such as, in the above-described embodiment, exemplified with the situation of illuminating part applying the present invention to lens, semiconductor substrate, FPD etc., but, also can be applied to the light accepting part of cmos sensor, solar cell etc.In addition, in the present embodiment, about the material of base material, hydrothermal conditions, utilize hydrothermal treatment consists to be formed micro concavo-convex the degree of depth, base material carried out to dry ecthing time condition etc., exemplified with several, but be not limited to these, certainly can carry out various distortion in the scope of thought of the present invention.
Symbol description
10,20: the parts with anti-reflective function
11,21: base material
13: antireflection film
14:Al
2o
3film
15: protuberance
16: recess
22: fine uneven portion
23:Al
2o
3film
24: micro concavo-convex shape Al
2o
3
Claims (16)
1. there are parts for anti-reflective function, it is characterized in that:
Comprise base material and be formed in the antireflection film on surface of described base material,
Described antireflection film carries out hydrothermal treatment consists by utilizing the hot water of high temperature or water vapor to the pellumina formed by atomic layer deposition method, is formed with minute concave-convex structure.
2. there are the parts of anti-reflective function as claimed in claim 1, it is characterized in that:
The substrate of use or flat-panel monitor is formed as optics or device.
3. there are the parts of anti-reflective function as claimed in claim 1 or 2, it is characterized in that:
Described pellumina is formed by alternative supply trimethyl aluminium and oxygenant.
4. there is a manufacture method for the parts of anti-reflective function, it is characterized in that, comprising:
Formed the operation of pellumina on the surface of base material by atomic layer deposition method; With
Utilize the hot water of high temperature or water vapor implement hydrothermal treatment consists to described pellumina and form minute concave-convex structure, make the operation of antireflection film.
5. there is the manufacture method of the parts of anti-reflective function as claimed in claim 4, it is characterized in that:
Described pellumina is formed by alternative supply trimethyl aluminium and oxygenant.
6. there are parts for anti-reflective function, it is characterized in that:
It is formed with the fine uneven portion with anti-reflective function on the surface of base material,
Described fine uneven portion is formed as follows: form pellumina on the surface of described base material, then, hydrothermal treatment consists is carried out to pellumina and forms micro concavo-convex shape aluminium oxide, then, with described micro concavo-convex shape aluminium oxide for etching mask carries out dry ecthing to the surface of described base material, and by described micro concavo-convex shape aluminium oxide removing.
7. there are the parts of anti-reflective function as claimed in claim 6, it is characterized in that:
The pellumina used when forming described fine uneven portion is formed by atomic layer deposition method.
8. parts with anti-reflective function as claimed in claims 6 or 7, is characterized in that:
The substrate of use or flat-panel monitor is formed as optics or device.
9. there is a manufacture method for the parts of anti-reflective function, it is characterized in that, comprising:
The operation of pellumina is formed on the surface of base material;
Utilize the hot water of high temperature or water vapor to implement hydrothermal treatment consists to described pellumina, form the operation of micro concavo-convex shape aluminium oxide; With
With described micro concavo-convex shape aluminium oxide for etching mask carries out dry ecthing to the surface of described base material, form fine uneven portion on the surface of described base material, and, by described micro concavo-convex shape aluminium oxide removing, form the operation of anti-reflection structure.
10. there is the manufacture method of the parts of anti-reflective function as claimed in claim 9, it is characterized in that:
The operation forming described pellumina is undertaken by atomic layer deposition method.
11. 1 kinds of parts with anti-reflective function, is characterized in that:
It is formed with the fine uneven portion with anti-reflective function on the surface of base material,
Described fine uneven portion is formed as follows: form refractive index, the etched easy etching film easier than base material near the refractive index with substrate on the surface of described base material, pellumina is formed on the surface of described easy etching film, then, hydrothermal treatment consists is carried out to pellumina and forms micro concavo-convex shape aluminium oxide, then, with described micro concavo-convex shape aluminium oxide for dry ecthing is carried out on the surface of etching mask to described easy etching film, and, by described micro concavo-convex shape aluminium oxide removing.
12. parts as claimed in claim 11 with anti-reflective function, is characterized in that:
The pellumina used when forming described fine uneven portion is formed by atomic layer deposition method.
13. parts with anti-reflective function as described in claim 11 or 12, is characterized in that:
Described base material is glass substrate, nesa coating or color filter.
14. 1 kinds of manufacture methods with the parts of anti-reflective function, is characterized in that, comprising:
The operation of the refractive index near the refractive index with substrate, etched easy etching film easier than base material is formed on the surface of base material;
The operation of pellumina is formed on the surface of described easy etching film;
The hot water of high temperature or water vapor is utilized to implement to described pellumina the operation that hydrothermal treatment consists forms micro concavo-convex shape aluminium oxide; With
With described micro concavo-convex shape aluminium oxide for dry ecthing is carried out on the surface of etching mask to described easy etching film, form fine uneven portion on the surface of described easy etching film, and, by described micro concavo-convex shape aluminium oxide removing, form the operation of anti-reflection structure.
15. manufacture methods as claimed in claim 14 with the parts of anti-reflective function, is characterized in that:
The operation forming described pellumina is undertaken by atomic layer deposition method.
16. manufacture methods with the parts of anti-reflective function as described in claims 14 or 15, is characterized in that:
Described base material is glass substrate, nesa coating or color filter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013254257A JP2015114381A (en) | 2013-12-09 | 2013-12-09 | Member with antireflection function and method of manufacturing member with antireflection function |
| JP2013-254257 | 2013-12-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104698512A true CN104698512A (en) | 2015-06-10 |
| CN104698512B CN104698512B (en) | 2017-09-01 |
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| Country | Link |
|---|---|
| JP (1) | JP2015114381A (en) |
| KR (1) | KR101833586B1 (en) |
| CN (1) | CN104698512B (en) |
| TW (1) | TWI632392B (en) |
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| CN107793041A (en) * | 2017-09-29 | 2018-03-13 | 广东星弛光电科技有限公司 | The preparation method of safety glass with wear-resisting alumina film plating layer |
| WO2019073111A1 (en) * | 2017-10-11 | 2019-04-18 | Aalto University Foundation Sr | A coating of an object |
| CN110600567A (en) * | 2018-05-25 | 2019-12-20 | 中国电子科技集团公司第十八研究所 | Total reflection glass cover plate for space solar cell and preparation method thereof |
| CN113678028A (en) * | 2019-03-27 | 2021-11-19 | 株式会社可乐丽 | Fine concave-convex pattern film and flat display device |
| CN114578462A (en) * | 2021-03-22 | 2022-06-03 | 浙江舜宇光学有限公司 | Optical imaging lens |
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| KR102388422B1 (en) * | 2017-08-30 | 2022-04-20 | 현대자동차주식회사 | Transparent substrate for vehicle and method for manufacturing vehicle |
| JP6794325B2 (en) * | 2017-08-31 | 2020-12-02 | 富士フイルム株式会社 | Conductive base material, manufacturing method of conductive base material, laminate and touch panel |
| JP7074849B2 (en) * | 2018-05-22 | 2022-05-24 | 富士フイルム株式会社 | Method for manufacturing a substrate with an uneven structure |
| US11714212B1 (en) * | 2020-09-14 | 2023-08-01 | Apple Inc. | Conformal optical coatings for non-planar substrates |
| CN113985504B (en) * | 2021-12-27 | 2022-04-26 | 诚瑞光学(苏州)有限公司 | Optical lens |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2015114381A (en) | 2015-06-22 |
| TWI632392B (en) | 2018-08-11 |
| TW201534956A (en) | 2015-09-16 |
| KR20150067057A (en) | 2015-06-17 |
| KR101833586B1 (en) | 2018-02-28 |
| CN104698512B (en) | 2017-09-01 |
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