CN102666909B - The manufacture method of nesa coating, the manufacture device of nesa coating, sputtering target and nesa coating - Google Patents
The manufacture method of nesa coating, the manufacture device of nesa coating, sputtering target and nesa coating Download PDFInfo
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- CN102666909B CN102666909B CN201080051495.0A CN201080051495A CN102666909B CN 102666909 B CN102666909 B CN 102666909B CN 201080051495 A CN201080051495 A CN 201080051495A CN 102666909 B CN102666909 B CN 102666909B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
Abstract
The present invention provides the manufacture method of a kind of nesa coating, it is not necessary to use steam just can form the nesa coating with good etching characteristic and conductive characteristic。The manufacture method of the nesa coating that embodiments of the present invention relate to includes: by sputtering target material thus forming the operation of indium and tin oxide film on substrate, wherein said target comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one element or its oxide selected from La, Nd, Dy, Eu, Gd, Tb, Zr, Al, Si, Ti and B；Etching solution is utilized to make the operation that described indium and tin oxide film is patterned；The operation of described indium and tin oxide film crystallization is made by heat treatment。Thus, film forming ito thin film in the near future can utilize weak acid to etch, and it is possible to give desired conductive characteristic to this ito film。
Description
Technical field
The present invention relates to the manufacture method of superior nesa coating, the manufacture device of nesa coating, sputtering target and the nesa coatings such as a kind of etching characteristic, conductive characteristic。
Background technology
In the manufacture field of flat faced display or solar electrical energy generation module, ITO (Indiumtinoxide) film that it is main component with Indium sesquioxide. and stannum oxide that nesa coating widely uses。Ito film is by the film forming such as vacuum vapor deposition, sputtering method, and in sputtering method, most cases uses the sputtering target being made up of ITO。
Owing under room temperature, the ito film of film forming is the state that crystalline mixes with noncrystalline matter, therefore, it is difficult to obtain desired electric conductivity。On the other hand, owing at the temperature of more than 200 DEG C, the ito film of film forming is crystalline state, therefore there is significantly high conductive characteristic。But, the ito film of crystallization dissolubility in the weak acid such as oxalic acid is low, it is necessary to use the strong acid such as hydrochloric acid or sulphuric acid as etching solution。Therefore, it is difficult to guarantee high etching selectivity between ito film and its counterdie or other wiring layers etc.。
Therefore, a kind of by mixing water steam in the sputter gas such as argon so that amorphous ito film film forming, then pass through ito film annealing so as to crystallization is thus making the method for low-resistance ito film by extensively known (with reference to patent documentation 1)。According to this method, owing to weak acid etching can be carried out under (deposition (as-deposition) state) after film forming, good etching characteristic therefore can be obtained。
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-179850 publication (paragraph [0023]～[0026])
Summary of the invention
But, there is problems with in the film build method of the ito film described in patent documentation 1, namely the impact of the steam owing to importing, makes the thin film being attached on the non-corrosive region preventing plate or target be easily peeled off, and becomes the reason producing granule。Further, due to the importing of steam, it is possible to hinder the stable scavenging action of film forming room。
In view of the above circumstances, it is an object of the invention to provide the manufacture method of a kind of nesa coating, it is not necessary to use steam just can form the nesa coating with good etching characteristic and conductive characteristic。
It addition, another object of the present invention is to provide the manufacture device of a kind of nesa coating and sputtering target, it is not necessary to use steam just can form the nesa coating with good etching characteristic and conductive characteristic。
In order to achieve the above object, the manufacture method of the nesa coating that embodiments of the present invention relate to includes: placement substrate in the cavity with target, described target comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one element or its oxide selected from lanthanum, neodymium, dysprosium, europium, gadolinium, terbium, zirconium, aluminum, silicon, titanium and boron；By sputtering described target, thus forming indium and tin oxide film on substrate。
In order to achieve the above object, the manufacture device of the nesa coating that embodiments of the present invention relate to includes: cavity, support portion, film forming portion。
Described cavity is configured to keep vacuum state。
Described support portion is at described cavity inner support substrate。
Described film forming portion has target, this target comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one element or its oxide selected from lanthanum, neodymium, dysprosium, europium, gadolinium, terbium, zirconium, aluminum, silicon, titanium and boron。Described film forming portion is by sputtering target material in described cavity, thus forming indium and tin oxide film on the substrate supported by described support portion。
In order to achieve the above object, the sputtering target that embodiments of the present invention relate to is the sputtering target for forming nesa coating on substrate through sputtering method, comprises the first component, second component, the 3rd component。
Described first component is made up of Indium sesquioxide.。
Described second component is made up of stannum oxide。
Described 3rd component is made up of at least one element or its oxide selected from lanthanum, neodymium, dysprosium, europium, gadolinium, terbium, zirconium, aluminum, silicon, titanium and boron。
In order to achieve the above object, the nesa coating that embodiments of the present invention relate to is the nesa coating on substrate through sputtering film-forming, comprises the first component, second component, the 3rd component。
Described first component is made up of Indium sesquioxide.。
Described second component is made up of stannum oxide。
Described 3rd component is made up of at least one element or its oxide selected from lanthanum, neodymium, dysprosium, europium, gadolinium, terbium, zirconium, aluminum, silicon, titanium and boron。
Accompanying drawing explanation
Fig. 1 indicates that the skeleton diagram manufacturing device of the nesa coating that embodiments of the present invention relate to；
Fig. 2 is the process flow chart that the manufacture method of the nesa coating that embodiments of the present invention are related to illustrates；
Fig. 3 illustrates the X-ray diffraction intensity distribution of the ito film that embodiments of the invention and comparative example relate to, and (A) is the measurement result about film forming ito film in the near future, (B) be about annealing after the measurement result of ito film；
Fig. 4 illustrates the relation between resistivity and the partial pressure of oxygen of the ito film that embodiments of the invention and comparative example relate to, (A) be about film forming after the measurement result of ito film, (B) be about annealing after the measurement result of ito film；
Fig. 5 indicates that the experimental result of the relation between etch-rate and the partial pressure of oxygen of the ito film that embodiments of the invention and comparative example relate to；
Fig. 6 indicates that the experimental result of the visible light transmitance of the ito film that embodiments of the invention and comparative example relate to。
Description of reference numerals
11 first cavitys
12 second cavitys
20 sputter cathodes
21 sputtering targets
22 magnet units
30 vacuum pumping systems
40 gas introduction parts
50 carriers
100 sputter equipments
101 film forming room
102 load/unload rooms
103 gate valves
Detailed description of the invention
The manufacture method of the nesa coating that embodiments of the present invention relate to includes: the operation of placement substrate in the cavity with target, wherein said target has and comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one element or its oxide selected from lanthanum, neodymium, dysprosium, europium, gadolinium, terbium, zirconium, aluminum, silicon, titanium and boron；By sputtering described target, thus forming indium and tin oxide film on substrate。
Manufacture method according to described nesa coating, it is possible to form amorphous indium and tin oxide film (hereinafter referred to as " ito film ") after film forming。Therefore, when making this ito film pattern by etching, it is possible to use the faintly acid etching solutions such as oxalic acid。Further, owing to easily guaranteeing high etching selectivity between counterdie or other distributions, good etching characteristic can therefore be obtained。
Further, described ito film crystallization is made by heat treatment (annealing), such that it is able to give good conductive characteristic。Owing to the ito film after heat treatment has good light transmission rate in visible light region, therefore nesa coating can be used as in flat faced display or solar electrical energy generation module etc. aptly。
The substrate being formed with ito film is usually glass substrate, in addition, it is also possible to be silicon substrate or ceramic substrate。Further, as long as there is thermostability under heat treatment temperature, it is possible to use organic substrate。
Described 3rd component is the element group that can form the ito film dissolving in weak acid。Especially by using dysprosium (Dy) or its oxide as described 3rd component, it is possible to obtain the ito film that conductive characteristic that resistivity is 300 μ below Ω cm is superior。
Gas for sputtering described target can be set to the mixing gas of argon and oxygen。Argon mainly generates the ion of sputtering target material。The effect of oxygen reacting property gas, adjusts the oxygen concentration of the ito film of film forming。By suitably adjusting partial pressure of oxygen, it is possible to form the ito film with desired conductive characteristic, etching characteristic。
For making the heat treatment temperature (annealing temperature) of ito film crystallization can be set to more than 200 DEG C。If heat treatment temperature is below 200 DEG C, then there is noncrystalline situation about mixing with crystallization in ito film。It addition, the upper limit of heat treatment temperature is not particularly limited, suitably can set according to the thermostability of the substrate etc. being formed with ito film。
On the other hand, the manufacture device of the nesa coating that embodiments of the present invention relate to includes: cavity, support portion, film forming portion。
Described cavity is configured to keep vacuum state。
Described support portion is at described cavity inner support substrate。
Described film forming portion has target, wherein this target comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one element or its oxide selected from La, Nd, Dy, Eu, Gd, Tb, Zr, Al, Si, Ti and B。Described film forming portion by sputtering described target in described cavity, thus forming indium and tin oxide film on the substrate supported by described support portion。
It addition, the sputtering target that embodiments of the present invention relate to is the sputtering target for forming nesa coating on substrate through sputtering method, comprise the first component, second component, the 3rd component。
Described first component is made up of Indium sesquioxide.。
Described second component is made up of stannum oxide。
Described 3rd component is made up of at least one element or its oxide selected from La, Nd, Dy, Eu, Gd, Tb, Zr, Al, Si, Ti and B。
Manufacture device according to described nesa coating, by sputtering the target (sputtering target) of described structure, it is possible to form amorphous ito film on substrate。Therefore, when making this ito film pattern by etching, it is possible to use the weak acid etching solutions such as oxalic acid。Further, owing to easily guaranteeing high etching selectivity between counterdie or other wiring layers, good etching characteristic can therefore be obtained。
Hereinafter, with reference to accompanying drawing, embodiments of the present invention are illustrated。
[sputter equipment]
Fig. 1 indicates that the skeleton diagram manufacturing device of the nesa coating that embodiments of the present invention relate to。The device of diagram is configured to the sputter equipment 100 for forming nesa coating。Sputter equipment 100 has: forms the film forming room 101 of nesa coating (ito film) F, load/unload room 102 on the surface of substrate S, connect the film forming room 101 gate valve 103 with load/unload room 102。
Film forming room 101 include having closed construction the first cavity 11, can to the vacuum pumping system 30 of the inner vacuum aerofluxus of the first cavity 11。Film forming room 101 be configured to can vacuum exhaust to the one-tenth film pressure of regulation, simultaneously can keep its vacuum。Vacuum pumping system 30 has main pump (turbomolecular pump (TurboMolecularPump, TMP)) 31, donkey pump (drum pump (RotaryPump, RP)) 32 to its back pressure side aerofluxus。
Film forming room 101 has sputter cathode 20。Sputter cathode 20 has sputtering target (being hereinafter referred merely to as " target ") 21, is used for the magnet unit 22 in the formation magnetic field, surface of target 21, applies the D/C power (diagram is omitted) of D/C voltage between target 21 and substrate S (and first cavity 11)。Target 21 as hereinafter described, is made up of indium tin oxide class material。Sputter cathode 20 is arranged at the bottom wall part of the first cavity 11 as the sputter cathode of DC magnetron-type。
Film forming room 101 has the gas introduction part 40 of the process gas (sputter gas) for importing sputtering in the inside of the first cavity 11。What gas introduction part 40 unshowned gas supply source, air-flow in pie graph adjusted valve etc. simultaneously constitutes gas delivery system。In the present embodiment, gas introduction part 40 is by argon (Ar) and oxygen (O2) mixing gas import the inside of the first cavity 11。In described mixed-gas atmosphere, the dividing potential drop of oxygen is such as 2.0E-3 (2.0 × 10-3) more than Pa 1.0E-2 (1.0 × 10-2) below Pa。
Film forming room 101 can also have for prevent on the inwall or other structures of the first cavity 11 adhere to filmogen prevent plate。Plate is prevented, such that it is able to suppress the pollution that the filmogen of the first cavity 11 causes, it is possible to improve the upkeep operation of film forming room 101 by arranging in film forming room 101。
Load/unload room 102 includes second cavity 12 with closed construction, and can to the vacuum pump 33 of the inner vacuum aerofluxus of the second cavity 12。Load/unload room 102 be configured to can vacuum exhaust to the vacuum of the pressure same degree in film forming room 101, its vacuum can be kept simultaneously。Though load/unload room 102 has the not shown family of power and influence, can join substrate S between inside and the outside of the second cavity 12 via this family of power and influence。When joining substrate S, make in load/unload room 102 as atmospheric pressure。
Present embodiment sputter equipment 100 also has the carrier 50 via gate valve 103 conveying substrate S between film forming room 101 and load/unload room 102。Carrier 50 is by not shown drive source, and on the guide rail (diagram is omitted) being set up on film forming room 101 and load/unload room 102, rectilinearity moves on the contrary。After the carrier 50 carried from load/unload room 102 to film forming room 101 comes and goes in film forming room 101, return to load/unload room 102。Substrate S is held in the lower surface of carrier 50, in film forming room 101, and film forming in this process of the surface by sputter cathode 20。
At this, substrate S uses glass substrate。The film forming face of substrate can also be the glass surface as base material, it is also possible to be the surface of the dielectric film formed on base material。Further, can also there is the metal wiring films such as copper on the surface of this dielectric film。
Wherein, carrier 50 constitutes " support portion " that support substrate S in the first cavity 11。Further, sputter cathode 20 and gas introduction part 40 constitute " film forming portion "。Described film forming portion is by sputtering target 21 in the first cavity 11, thus forming indium and tin oxide film on the substrate S that carrier 50 supports。Further, constitute the magnet unit 22 of sputter cathode 20, D/C power etc. and constitute " plasma produces mechanism "。Plasma produces mechanism and is fed to sputter gas (Ar and the O in the first cavity 11 by generation from gas introduction part 402Mixing gas) plasma, thus being formed for the ion of sputtering target 21。
[target]
It follows that the details for target 21 illustrate。
Target 21 is configured to target or sputtering target for forming nesa coating F on substrate S through sputtering method。Target 21 is the sintered body of the discoideus or rectangular plate-like being made up of indium tin oxide (hereinafter referred to as " ITO ") class material, and its sintered density is such as more than 98%。
Target 21 of the present embodiment comprises by Indium sesquioxide. (In2O3) the first component of forming, the second component being made up of stannum oxide (SnO), and the 3rd component as additive。3rd component is chosen from least one element or its oxide of lanthanum (La), neodymium (Nd), dysprosium (Dy), europium (Eu), gadolinium (Gd), terbium (Tb), zirconium (Zr), aluminum (Al), silicon (Si), titanium (Ti) and boron (B)。3rd components be soluble, in acid, can form amorphous ito film after the film was formed soon。
The target 21 of described structure by sputtering in film forming room 101, thus forming the ito film F including described first, second and third component on substrate S。Therefore, the composition of target 21 suitably can adjust according to the composition of the ito film F answering film forming。The oxygen concentration of ito film F can also be adjusted by the partial pressure of oxygen in the film forming room 101 in film forming。
Generally, the weight ratio between Indium sesquioxide. (the first component) and stannum oxide (second component) is 9: 1, but is in addition such as adjusted in the scope of 97.5: 2.5～85: 15。Further, the addition of additive (the 3rd component), when addition element is α, represents by below equation (1)。
0.1≤{ α/(In+Sn+ α) }≤10 [atom %] (1)
It addition, when addition element is oxide, when setting this oxide as α Ox, addition below equation (2) represents。
0.06≤{αOX/(In2O3+SnO+αOx)≤6 [atom %] (2)
When the addition of the 3rd component is less than 0.1 atom %, it is very unstable to form amorphous ito film。Namely, it is possible to form the ito film that crystalline mixes with noncrystalline matter。On the other hand, when the addition of the 3rd component is more than 10 atom %, the ito film obtained is difficult to obtain the character such as desired conductive characteristic or light transmission rate。The addition of the 3rd component is different according to the kind of the element used, but can select in above-mentioned scope。
By using the target 21 of described structure, such that it is able to make amorphous indium and tin oxide film (ito film) F film forming on substrate S。Owing to film forming ito film F in the near future is non-crystalline state, therefore when making ito film pattern, it is possible to use the faintly acid etching solution such as oxalic acid or acetic acid。Further, after patterning, by annealing, (heat treatment) makes ito film F crystallization, such that it is able to obtain the ito film F that resistivity is low, electric conductivity is excellent。
[manufacture method of nesa coating]
It follows that the manufacture method for nesa coating of the present embodiment illustrates。Fig. 2 illustrates its process flow。The manufacture method of present embodiment nesa coating includes: the film formation process (step ST1) of ito film F, the patterning operation (step ST2) of ito film F, ito film F annealing operation (step ST3)。
(film formation process)
In the film formation process (step ST1) of ito film F, use the sputter equipment 100 shown in Fig. 1。With reference to Fig. 1, the substrate S being loaded in load/unload room 102 is held in the lower surface of carrier 50。Then, drive vacuum pump 33, be exhausted in load/unload room 102。When the pressure of load/unload room 102 reaches same degree with the pressure (being such as 0.67Pa) of film forming room 101, open gate valve 103, carrier 50 is delivered in film forming room 101。From load/unload room 102 to film forming room 101 delivery vehicles 50, inaccessible gate valve 103。It is delivered to the rectilinearity in film forming room 101 of the carrier 50 in film forming room 101 to move。Substrate S while moving together with carrier 50, by sputter cathode 20 film forming。
Sputter gas (Ar+O is imported with the flow of regulation from gas introduction part 40 in film forming room 1012)。The sputter gas imported is encouraged by the DC electric field being applied between target 21 and carrier 50 and the fixed magnetic field formed on target 21 surface by magnet unit 22, thus produces the plasma of sputter gas。Ion (particularly Ar ion) in plasma is attracted to sputter cathode 20 by the effect of electric field, thus the surface of target 21 is sputtered。ITO particle is pounded out from the surface of target 21 by the sputtering effect of ion, and by adhering to, being deposited on the surface of the substrate S relative with target 21, thus form ito film F on the surface of substrate S。Further, the oxygen comprised in sputter gas produces highly active oxygen-derived free radicals, and the ITO particle that the oxygen-derived free radicals of generation is pounded out with the surface from target 21 reacts。Therefore, the oxygen concentration of ito film F substrate S formed is controlled by the amount of oxygen in sputter gas。
In the present embodiment, passing through substrate S film forming above target 21, it is so-called by the mode of film forming namely to adopt。In the present embodiment, substrate S carrier 50 in travelling to and fro between film forming room 101 go to film forming on path, but be not limited to this, it is also possible to film forming on the return path of carrier 50, it is also possible to going to film forming on both path and return path。Further, substrate S is transferred under without heating (room temperature) in film forming room 101 but it also may as required, built-in heating source in sputter equipment 100, by substrate heating to set point of temperature during film forming。
After ito film F film forming completes, substrate S carries to load/unload room 102 via gate valve 103 together with carrier 50。Then, gate valve 103 is inaccessible, and load/unload room 102 is to atmosphere opening, and substrate S film forming completed via the not shown family of power and influence is taken out to outside。As it has been described above, on the surface of substrate S to amorphous ito film F film forming。
(patterning operation)
In patterning operation (step ST2), wet etching is utilized to make ito film F be patterned as regulation shape。Before this, ito film F forms Etching mask。In etching work procedure, from Etching mask to the surface-coated etching solution of substrate S, thus dissolving the ito film F that the peristome from Etching mask exposes。Then, through the cleaning of substrate S, drying process, the patterning operation of ito film F is completed。
According to present embodiment, it is non-crystalline state owing to using the ito film F that sputter equipment 100 manufactures, therefore in the patterning operation of this ito film F, can use the weakly acidic etching solution (reagent (ITO-05N, ITO-06N, ITO-07N) (above for trade name) that such as, oxalic acid or Northeast chemical company (chemistry society) manufacture) containing oxalic acid that ito film F is etched。Thus, it is easy between the counterdie metallic wiring layer etc. of ito film F, guarantee high etching selectivity, therefore can obtain good etching characteristic。Further, confirmation can suppress ito film F to produce etch residue when patterning。
The patterned shape of ito film F is different according to the kind of manufactured device。Such as, in the pixel electrode situation that ito film is used for liquid crystal display, ito film F is patterned in units of pixel。It addition, when ito film is used for solar electrical energy generation module, ito film F patterns in units of each generator unit。
(annealing operation)
Annealing operation (step ST3), by the ito film F of patterning is annealed (heat treatment), makes ito film F crystallization。The purpose making ito film F crystallization is in that to reduce the resistivity of ito film F, improve conductive characteristic。
In the annealing operation of ito film F, it is common to use heat-treatment furnace。Annealing conditions can suitably set, for instance, it is possible to it is set in air, more than 200 DEG C。When annealing temperature is less than 200 DEG C, there is crystallization and noncrystalline situation about mixing in ito film F。Further, the upper limit of annealing temperature is not particularly limited, and can be appropriately configured according to the thermostability of other functional films (dielectric film, metal film) beyond substrate S, ito film F or the ito film F formed on substrate S。Annealing atmosphere is not limited to air, for instance can also be blanket of nitrogen。Annealing time sets according to annealing temperature, and generally, annealing temperature is more high, sets annealing time more short。
As it has been described above, manufacture nesa coating of the present embodiment (ito film F)。Present embodiment nesa coating comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one element or its oxide selected from La, Nd, Dy, Eu, Gd, Tb, Zr, Al, Si, Ti and B。
Manufacture method according to present embodiment nesa coating, can form amorphous ito film F after film forming。Especially, according to present embodiment, it is not necessary to add steam in sputter gas and just can manufacture amorphous ito film。Accordingly it is possible to prevent due in sputter gas add steam and with occur harmful effect, such as be attached to the ito film preventing on plate be easily peeled off and cause granule generation, hinder film forming room 101 stable scavenging action thus causing the instability etc. of sputtering pressure。
Further, according to present embodiment, when passing through to etch the ito film patterning making film forming, it is possible to use the faintly acid etching solutions such as oxalic acid。Thus, it is easy between counterdie or other wiring layers, guarantee high etching selectivity, good etching characteristic can therefore be obtained。
Further, according to present embodiment, owing to making ito film F crystallization by heat treatment (annealing), the ito film F with good conductive characteristic can therefore be manufactured。The ito film F so manufactured has good light transmission rate in visible light region, therefore can be used as the nesa coating of flat faced display or solar electrical energy generation module etc. aptly。
Embodiment
(embodiment 1)
Manufacture the sputtering target (hereinafter also referred to " the ITO target that Dy adds ") of a kind of dysprosium oxide adding 1.5 atom % in indium tin oxide。Using the ITO target that this Dy adds, sputter equipment as shown in Figure 1 forms thickness on base materialIto film (hereinafter also referred to " Dy add ito film ")。It is 600W (1.16W/cm that membrance casting condition is set to DC power2), distance (T/S distance) between target and substrate be 100mm, magnet unit magnetic field be sized to 300G, rate of film build (dynamic rate) isSputter gas uses the mixing gas of argon and oxygen, makes partial pressure of oxygen different thus forming multiple ito film sample。Wherein, argon partial pressure is set to 0.67Pa (200sccm), partial pressure of oxygen be set to 0Pa, 1.33 × 10-3Pa、2.66×10-3Pa、5.32×10-3Pa、7.98×10-3Pa、1.06×10-2Pa。
To being 5.32 × 10 at partial pressure of oxygen-3The ito film sample manufactured under Pa, the X-ray diffraction intensity of mensuration。Determinator employs " Rinto (trade name) " that company of science (society of science) manufactures。Then, to each ito film sample determination etch-rate manufactured。Etching solution employs the reagent (" ITO-06N " (trade name) that Northeast chemical company manufactures) containing oxalic acid。It follows that in atmosphere, 230 DEG C, 1 hour when each ito film sample has been made annealing treatment。After annealing, to each ito film sample determination X-ray diffraction intensity, resistivity and visible light (wavelength 400nm～800nm) transmitance。The mensuration of resistivity employs " LorestaMCP-T350 (trade name) " that Mitsubishi Chemical Ind manufactures。It is 5.32 × 10 that the mensuration of X-ray diffraction intensity and visible light transmitance employs respectively at partial pressure of oxygen-3The ito film sample manufactured under Pa。The mensuration of visible light transmitance employs " U-4100 " that Hitachi, Ltd manufactures。
(embodiment 2)
Manufacture the sputtering target (hereinafter also referred to " the ITO target that B adds ") of a kind of boron oxide compound adding 1 atom % in indium tin oxide。This B ITO target added is used to form ito film (hereinafter also referred to " ito film that B adds ") under the same conditions as example 1。For the B of the film forming ito film added, measure the X-ray diffraction intensity before and after etch-rate, resistivity, light transmission rate and annealing under the same conditions as example 1 respectively。
(comparative example 1)
Manufacture the sputtering target (hereinafter also referred to " the ITO target that Ce adds ") of a kind of cerium oxide adding 5 atom % in indium tin oxide。This Ce ITO target added is used when identical, to form ito film (hereinafter also referred to " ito film that Ce adds ") with embodiment。For the Ce of the film forming ito film added, measure the X-ray diffraction intensity before and after etch-rate, resistivity, light transmission rate and annealing under the same conditions as example 1 respectively。
(comparative example 2)
In the sputter gas containing argon, oxygen and steam, the ITO target containing indium oxide with tin-oxide is made to sputter, thus forming ito film on substrate (hereinafter also referred to " H2The ito film that O adds ")。Membrance casting condition is identical with embodiment 1, makes the partial pressure of oxygen in sputtering pressure different thus forming multiple ito film。Wherein, argon partial pressure is set to 0.67Pa, and steam partial pressure is set to 2.66 × 10-3Pa, partial pressure of oxygen be set to 0Pa, 1.33 × 10-3P、2.66×10-3Pa、5.32×10-3Pa。H for film forming2The ito film that O adds, under the same conditions as example 1, measures the X-ray diffraction intensity before and after etch-rate, resistivity, light transmission rate and annealing respectively。It is 1.33 × 10 that the mensuration of visible light transmitance employs at partial pressure of oxygen-3The ito film sample manufactured under Pa。
Fig. 3 (A) illustrates the ito film and H that ito film that ito film that Dy adds, B add, Ce add2The ito film that O adds X-ray diffraction intensity before annealing, Fig. 3 (B) illustrates the X-ray diffraction intensity after its annealing。As shown in Fig. 3 (A), it is believed that TIO film before annealing, the i.e. X-ray diffraction pattern of film forming ito film in the near future indicate that the halation pattern of non-crystalline state。Further, as shown in Fig. 3 (B), under the angle of diffraction that ITO crystallization is intrinsic, think intensity peak, thereby confirm that the ito film after annealing is crystalline state。
It follows that Fig. 4 (A), (B) indicate that before annealing with annealing after the experimental result of resistivity of each ito film sample, before Fig. 4 (A) illustrates annealing, after Fig. 4 (B) illustrates annealing。For each figure in figure, " ◆ " represents H2Ito film, " ■ " that O adds represent the Ce ito film added, " ▲ " represent the Dy ito film added, and, "●" represents the B ito film (in Figure 5 too) added。
For any one in Dy ito film, the ito film of B interpolation and the ito film of Ce interpolation added, before comparing annealing after confirming annealing, less resistivity can be obtained。This is owing to the resistivity ratio non-crystalline state under crystalline state is lower。Resistivity after annealing, for any ito film sample, is 5.32 × 10 at partial pressure of oxygen-3During Pa minimum, for Dy add ito film and Ce add ito film be about 300 μ Ω cm, for B add ito film be about 400 μ Ω cm。
On the other hand, for H2The ito film that O adds, after being identified through annealing, is 1.33 × 10 at partial pressure of oxygen-3The minima (about 300 μ Ω cm) of resistivity can be obtained during Pa。Namely, it is believed that the resistivity of the ito film that the ito film of Dy interpolation and Ce add, have and H2The suitable value of ito film that O adds。
It follows that Fig. 5 indicates that the experimental result of the etch-rate of amorphous each ito film sample。Confirm that the Dy ito film added has and H2The equal etch-rate of ito film that O adds。Confirm that the etch-rate of the B ito film added compares H2The etch-rate of the ito film that O adds is high。On the other hand, for the Ce ito film added, confirm that etch-rate compares H2The ito film that O adds is low。It is thought that because comparing Dy oxide or B oxide, Ce oxide is difficult to be dissolved in the reason of weak acid。
Further, Fig. 6 indicates that the experimental result of the visible light transmitance of each ito film after annealing。For the ito film that the Dy ito film added and B are added, confirm have and H2The equal visible light transmitance (more than 90%) of ito film that O adds。On the other hand, for the Ce ito film added, confirm that other ito film of the suppression ratio of transmitance are notable within the scope of 500nm～600nm。
As it has been described above, the ito film that the ito film added of the Dy related to according to the present embodiment and B add, it is possible to obtain with H2The equal etch-rate of ito film that O adds, resistivity, visible light transmitance。Further, the sputtering target by using the Dy sputtering target added or B to add, it is possible to stably film forming obtains the ito film that patterned property, conductive characteristic and light transmission features are superior。
Above, being illustrated for embodiments of the present invention, certainly, the present invention is also defined in this, and the technological thought based on the present invention can implement various deformation。
Such as, in embodiment of above, the Dy addition in the Dy sputtering target added is set to 1.5 atom %, the addition of the B in the B sputtering target added is set to 1 atom %, but is not limited to this。Owing to the addition of these the 3rd components is different, the etch-rate of the ito film obtained, resistivity, visible light transmitance etc. change, and therefore according to required characteristic, addition suitably can be adjusted。
Claims (6)
1. the manufacture method of a nesa coating, it is characterised in that including:
Placement substrate in the cavity with target, wherein said target comprises the first component being made up of Indium sesquioxide., the second component being made up of stannum oxide, and the 3rd component being made up of at least one oxide selected from lanthanum, neodymium, dysprosium, europium, gadolinium, terbium, zirconium, aluminum, silicon, titanium and boron, addition (the α O of described 3rd componentx) represent with following formula:
0.06≤{αOx/(In2O3+SnO+αOx)≤6 [atom %],
The weight ratio of described first component and described second component is In2O3: SnO=97.5:2.5～85:15；
By sputtering described target, thus forming amorphous indium and tin oxide film on substrate；
Use the etching solution comprising oxalic acid that described indium and tin oxide film is patterned；
Described indium and tin oxide film crystallization is made by heat treatment。
2. the manufacture method of nesa coating according to claim 1, it is characterised in that described 3rd component is dysprosium oxide。
3. the manufacture method of nesa coating according to claim 1, it is characterised in that described 3rd component is boron oxide compound。
4. the manufacture method of the nesa coating according to Claims 2 or 3, it is characterised in that described target is sputtering in the not steam-laden argon mixed-gas atmosphere with oxygen。
5. the manufacture method of nesa coating according to claim 4, it is characterised in that in described mixed-gas atmosphere, the dividing potential drop of oxygen is more than 2.0E-3Pa below 1.0E-2Pa。
6. the manufacture method of the nesa coating according to Claims 2 or 3, it is characterised in that the heat treatment temperature making described indium and tin oxide film crystallization is more than 200 DEG C。
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| JP2013012409A (en) * | 2011-06-29 | 2013-01-17 | Toshiro Kuji | Generation method of transparent conductive film and transparent conductive film generation device |
| CN102651251A (en) * | 2012-05-29 | 2012-08-29 | 番禺南沙殷田化工有限公司 | Low-temperature crystallization indium tin oxide (ITO) transparent conducting film and preparation method of low-temperature crystallization ITO transparent conducting film |
| CN102945694B (en) * | 2012-11-08 | 2015-05-20 | 深圳南玻显示器件科技有限公司 | ITO (indium tin oxide) base plate and preparation method of ITO base plate |
| KR102061790B1 (en) | 2013-02-05 | 2020-02-12 | 삼성디스플레이 주식회사 | Manufacturing method for transparent electrode and an organic light emitting display using the transparent electrode |
| JP5805799B2 (en) * | 2013-05-15 | 2015-11-10 | 日本写真印刷株式会社 | Touch sensor and touch sensor module |
| US9988707B2 (en) * | 2014-05-30 | 2018-06-05 | Ppg Industries Ohio, Inc. | Transparent conducting indium doped tin oxide |
| CN104746003B (en) * | 2014-12-24 | 2017-09-26 | 信利（惠州）智能显示有限公司 | Tin indium oxide low temperature film plating process |
| JP6553950B2 (en) * | 2015-05-27 | 2019-07-31 | 日東電工株式会社 | Transparent conductive film and method for producing the same |
| TWI664646B (en) * | 2016-09-12 | 2019-07-01 | 日商愛發科股份有限公司 | Method of manufacturing transparent-conductive-film-attached substrate, apparatus of manufacturing transparent-conductive-film-attached substrate, and transparent-conductive-film-attached substrate |
| CN106893132B (en) * | 2017-03-30 | 2019-11-15 | 维沃移动通信有限公司 | A kind of organic cambered shell processing method and organic cambered shell |
| KR102268160B1 (en) * | 2017-05-15 | 2021-06-21 | 미쓰이금속광업주식회사 | Sputtering target for transparent conductive film |
| CN110741106A (en) * | 2017-08-08 | 2020-01-31 | 三井金属矿业株式会社 | Oxide sintered body and sputtering target |
| CN108149210B (en) * | 2017-12-26 | 2019-12-31 | 哈尔滨工业大学 | Preparation method of long-wave infrared anti-reflection protective film |
| JP7112854B2 (en) * | 2018-02-19 | 2022-08-04 | 住友化学株式会社 | tin oxide powder |
| WO2021240962A1 (en) * | 2020-05-25 | 2021-12-02 | 日東電工株式会社 | Method for producing light-transmitting conductive sheet |
| CN117229051A (en) * | 2023-09-21 | 2023-12-15 | 株洲火炬安泰新材料有限公司 | LaTb co-doped ITO target material and preparation method and application thereof |
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