WO2017073388A1 - インプリント装置 - Google Patents
インプリント装置 Download PDFInfo
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- WO2017073388A1 WO2017073388A1 PCT/JP2016/080671 JP2016080671W WO2017073388A1 WO 2017073388 A1 WO2017073388 A1 WO 2017073388A1 JP 2016080671 W JP2016080671 W JP 2016080671W WO 2017073388 A1 WO2017073388 A1 WO 2017073388A1
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- condensable gas
- mold
- pattern
- condensable
- gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/002—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/70858—Environment aspects, e.g. pressure of beam-path gas, temperature
- G03F7/70866—Environment aspects, e.g. pressure of beam-path gas, temperature of mask or workpiece
- G03F7/70875—Temperature, e.g. temperature control of masks or workpieces via control of stage temperature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/021—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface
- B29C2043/023—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface having a plurality of grooves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/56—Compression moulding under special conditions, e.g. vacuum
- B29C2043/561—Compression moulding under special conditions, e.g. vacuum under vacuum conditions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
Definitions
- the present invention relates to an imprint apparatus, and more particularly to a nanoimprint apparatus that performs transfer at a nano-level high resolution.
- nanoimprints there are known thermal imprints in which a concavo-convex pattern is transferred by heat using a thermoplastic resin, and optical imprints in which a concavo-convex pattern is transferred by ultraviolet rays using a photocurable resin.
- Such a nanoimprint is economical because a nanostructure can be easily and repeatedly formed once a mold is produced, and a high throughput can be obtained.
- it is a processing technology with little harmful waste, in recent years it is expected to be applied not only to semiconductor devices but also to various fields such as bit patterned media used in next-generation hard disks.
- the compressed air taken in the compressed state not only stays uniformly in the mold recess, but also inhibits the flow of the resin and lowers the energy of the resin surface. In other words, a missing portion is formed in the pattern portion on the resist layer after completion of the transfer operation, which causes a decrease in transfer accuracy.
- a robust working chamber that can withstand the vacuum is required.
- the pressure for pressing the mold is excessively increased, the mold itself is deformed, and high-precision transfer cannot be performed. In the worst case, the mold and the substrate material may be damaged.
- Patent Document 1 the present inventors supply a condensable gas into the working chamber, and condense the condensable gas contained even with a relatively low mold pressing pressure.
- a technique for preventing a decrease in transfer accuracy due to the incorporation of a gas forming an imprint work atmosphere is proposed. That is, the temperature at which the resist layer enters the recess formed in the mold and the pressure in the recess when transferring the imprint formed on the mold to the resist layer applied on the substrate surface or the supplied resist.
- the vapor pressure of this gas at room temperature is set to 0.05 MPa or more and 1.00 MPa or less.
- the present inventors have disclosed 1,1,1,3,3 pentafluoropropane (a kind of condensable gas) between the resin and the mold in Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3.
- the relationship between the gas flow rate (ratio of gas to the atmosphere) and the filling rate of the resist into the mold can be clarified, the viscosity of the resin before curing can be reduced, and the mold and after curing It has been reported that it is possible to reduce the force (release force) that separates the resin.
- the present inventors performed nanoimprinting in an atmosphere in which one type of pentafluoropropane, which is a condensable gas, and helium gas are mixed, whereby the surface roughness of the formed pattern, the release force, It has been reported that the filling speed of the resist into the mold can be adjusted.
- capillary condensation occurs due to the influence of capillary force acting on a fine space.
- the vapor in the micropore tends to become liquid compared to the vapor outside the micropore due to the capillary force, and this phenomenon is called capillary condensation.
- Patent Document 1 when a condensable gas having a low saturated vapor pressure is used, the possibility of capillary condensation occurring compared to water or the like increases.
- the photocurable resin is filled into the groove portion of the mold by capillary condensation.
- the condensable gas may condense, resulting in poor filling of the resist, resulting in poor formation patterns.
- an object of the present invention is to prevent resist filling failure due to capillary condensation and to enable adjustment of the pattern line width and shape even when the same mold is used.
- V molar volume of condensable gas liquid 100.7 ⁇ 10 ⁇ 6 m 3 / mol
- ⁇ Condensable gas surface tension of 0.0133 N / m (20 ° C)
- R Gas constant 8.31m 2 kg / s 2 Kmol
- T Temperature 293.15K (20 ° C)
- atmospheric pressure process When p is considered, the actual vapor pressure is 101.3 kPa.
- the capillary radius a ⁇ 10.82 nm is obtained by assuming that the contact angle ⁇ is 0 ° and substituting this into the equation (2). When considered as the diameter of the hole pattern, it is 2a, and 21.64 nm is obtained.
- FIG. 1 shows a graph summarizing the diameter of the hole pattern in which capillary condensation occurs for each of various condensable gases having different saturated vapor pressures.
- the first condensable gas with a saturated vapor pressure of 0.05 MPa or more and less than 0.2 MPa at room temperature shows a hole pattern diameter of 10 nm or more that causes capillary condensation, and it can be seen that a single gas is affected by capillary condensation.
- the second condensable gas having a saturated vapor pressure of 0.2 MPa or more and 1 MPa or less at normal temperature is not affected by capillary condensation at a pattern size of 5 nm to several 100 nm, which is expected to be applied for nanoimprinting.
- the resist layer penetrates into the recess formed in the mold and condenses by the temperature and pressure inside the recess sealed with the resist layer.
- a supply device is provided that supplies a plurality of condensable gases having different saturated vapor pressures at a certain ratio as the condensable gas. I made it.
- the condensation reaction occurs in the entire region without being affected by capillary condensation, and the transfer accuracy is reduced.
- the width of the nanoimprinted pattern can be changed arbitrarily by arbitrarily controlling the mixed gas atmosphere with different saturated vapor pressures. Once a single mold is produced, various line widths can be obtained. It is possible to create a transfer pattern.
- FIG. 1 is a graph summarizing the diameters of hole patterns in which capillary condensation occurs for each condensable gas having a different saturation vapor pressure.
- FIG. 2 shows the gas of the first condensable gas (trans-1-chloro-3,3,3-trifluoropropene gas) and the second condensable gas (trans-1,3,3,3-tetrafluoropropene). And a hole pattern diameter in which capillary condensation occurs.
- FIG. 3 is a diagram illustrating an outline of the nanoimprint apparatus according to the present embodiment.
- FIG. 1 is a graph summarizing the diameters of hole patterns in which capillary condensation occurs for each condensable gas having a different saturation vapor pressure.
- FIG. 2 shows the gas of the first condensable gas (trans-1-chloro-3,3,3-trifluoropropene gas) and the second condensable gas (trans-1,3,3,3-tetrafluoropropene). And a hole pattern diameter in which ca
- FIG. 4 shows a mold structure in which the straight groove width is 70 nm and the groove depth is 100 nm in the photocurable resin 2 on the substrate 1 in the atmosphere of the first condensable gas 50% and the second condensable gas 50%. It is the electron microscope image of the pattern which transcribe
- FIG. 5 shows a mold structure in which the straight groove width is 125 nm and the groove depth is 100 nm in the photocurable resin 2 on the substrate 1 in the atmosphere of the first condensable gas 50% and the second condensable gas 50%. It is the electron microscope image of the pattern which transcribe
- FIG. 5 shows a mold structure in which the straight groove width is 70 nm and the groove depth is 100 nm in the photocurable resin 2 on the substrate 1 in the atmosphere of the first condensable gas 50% and the second condensable gas 50%. It is the electron microscope image of the pattern which transcribe
- FIG. 6 is a graph of the line width of a pattern obtained by transferring a mold structure having a straight groove width of 70 nm and a groove depth of 100 nm in an atmosphere in which the mixing conditions of the first condensable gas and the second condensable gas are changed. It is.
- FIG. 7 is a graph of the line width of a pattern obtained by transferring a mold structure having a straight groove width of 125 nm and a groove depth of 100 nm in an atmosphere in which the mixing conditions of the first condensable gas and the second condensable gas are changed. It is.
- trans-1-chloro-3,3,3-trifluoropropene saturated vapor pressure at 20 ° C. of 0.107 MPa
- trans-1,3,3,3-tetrafluoropropene 20 ° C. of 0.107 MPa
- FIG. 2 shows a graph of the ratio of the mixed gas and the diameter of the hole pattern in which capillary condensation occurs when a saturated vapor pressure at 19 ° C. of 0.419 MPa) is mixed as the second condensable gas.
- the second condensable gas with respect to the first condensable gas is 5 nm or less of the diameter of the hole pattern in which capillary condensation occurs Nanoimprinting may be performed under the condition that the ratio of the ratio is 35% or more.
- FIG. 3 is a diagram illustrating an outline of the nanoimprint apparatus according to the present embodiment.
- the imprint apparatus presses the mold 3 on which a fine pattern is formed against the photocurable resin 2 formed in a molten state on the substrate 1 and puts the photocurable resin 2 in a state where both are in contact with each other.
- the pattern is transferred onto the substrate 1 by curing.
- Such an imprint apparatus is used, for example, for manufacturing a semiconductor device and a microsensor.
- silicon or glass is used as the substrate 1, and glass, transparent resin, or the like is used as the mold 3.
- the method for forming the photocurable resin 2 on the substrate 1 include, but are not limited to, a spin coater, a dispenser, an inkjet, a bar coater, an applicator, and a spray coater.
- the photocurable resin 2 acrylic, epoxy, silicone, phenol and the like are used.
- the photocurable resin 2 is not limited to this as long as it is a photocurable resin composition.
- an imprint transfer method a method of transferring a pattern in a batch using a mold 3 having a pattern that is almost the same size as the substrate, and a step-and-step of transferring a pattern multiple times using a mold having a pattern smaller than the substrate. Examples include a repeat method and a roll type method in which a pattern is continuously transferred using a cylindrical mold, but the transfer method using a mold or a mold is not limited thereto.
- nozzles 4 a and 4 b are installed. From the first condensable gas tank 6 and the second condensable gas tank 7 through the condensable gas supply pipe 5. The first condensable gas and the second condensable gas are supplied at a constant ratio via the adjusting valves 6a and 7a.
- the method of supplying a plurality of condensable gases to the space formed between the substrate 1 and the mold 3 is very simple as a method for creating a high-concentration mixed gas environment. The method is not limited to this as long as it can create a mixed atmosphere between the substrate 1 and the mold 3 such as a method of making the imprint space a closed space.
- PAK-01 manufactured by Toyo Gosei Co., Ltd.
- NTT-AT NTT-AT
- Imprinting conditions are a pressure of 0.1 MPa, a pressing time of 10 seconds, a UV irradiation intensity of 100 mJ / cm 2 , and an irradiation time of 1 second.
- trans-1-chloro-3,3,3-trifluoropropene having a saturated vapor pressure of 0.107 MPa at 20 ° C. is used, and the saturated vapor pressure at 20 ° C. is used as the second condensable gas.
- Trans-1,3,3,3-tetrafluoropropene of 0.419 MPa was used.
- the ratio of the first condensable gas and the second condensable gas is set while adjusting the flow rates by the adjusting valves 6a and 7a so that the total flow rate of the first condensable gas and the second condensable gas is maintained at 2000 sccm.
- the nanoimprint was performed 5 times, changing by 25%.
- the first time is 100% first condensable gas, 0% second condensable gas
- the second time is 75% first condensable gas, 25% second condensable gas
- the third time is 50% first condensable gas
- the second condensable gas is 50%
- the fourth time is the first condensable gas 25%
- the fifth time is the first condensable gas 0% and the second condensable gas 100%.
- some inevitable components such as nitrogen and oxygen are included.
- the shape of the pattern formed by imprinting was observed using an electron microscope (FE-SEM). Then, based on the acquired image file, two line patterns were extracted, and the average line width of the pattern was calculated using a line width determination program.
- FE-SEM electron microscope
- the pattern in FIG. 4 is a mold structure with a straight groove width of 70 nm and a groove depth of 100 nm
- the pattern in FIG. 5 is a transfer of a mold structure with a straight groove width of 125 nm and a groove depth of 100 nm. . In each case, the pattern is formed satisfactorily without any pattern defects such as bubble defects.
- FIG. 6 is a graph of the line width of a pattern obtained by transferring a mold structure having a straight groove width of 70 nm and a groove depth of 100 nm in an atmosphere in which the mixing conditions of the first condensable gas and the second condensable gas are changed. Indicates. When the proportion of the second condensable gas is 0% (the first condensable gas is 100%), the line width of the imprinted pattern is the smallest, and conversely, the second condensable gas is 100% (the first condensable gas) The line width of the imprinted pattern was the largest when the property gas was 0%.
- FIG. 7 shows a graph of the line width of a pattern obtained by transferring a mold structure having a straight groove width of 125 nm and a groove depth of 100 nm under an atmosphere in which the mixing conditions of the first and second condensed gases are changed. In the same manner as described above, it was possible to confirm a variation in line width with high linearity depending on the ratio of the second gas.
- Substrate 2 Photocurable resin 3: Mold 4a, 4b: Nozzle 5: Condensable gas supply pipe 6: First condensable gas tank 7: Second condensable gas tank 6a, 7a: Adjustment valve
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Abstract
Description
このような中、半導体デバイスのパターンを作製するためのリソグラフィ技術は、パターンの微細化が進むにつれ、露光装置などが極めて高価になってきている。
このように高価となってきたリソグラフィ技術の代替技術として、装置価格や使用材料などが安価でありながら、10nm程度の高解像度を有する微細パターン形成が可能なナノインプリントが注目されている。
このようなナノインプリントは、一度モールドを作製すれば、ナノ構造が簡単に、しかも、繰り返して成型できるため、高いスループットが得られて経済的である。さらに、有害な廃棄物が少ない加工技術であるため、近年、半導体デバイスに限らず、次世代ハードディスクに用いられるビットパターンドメディアなど、さまざまな分野への応用が期待されている。
その対策として、インプリント技術でモールドをレジストに押圧する工程を真空中で行う方法や、モールドを押圧する圧力を非常に大きくすることで、取り込まれた大気の体積を減少させることが考えられる。
しかし、レジストに押圧する工程を真空中で行うためには、真空に耐え得る頑強な作業室が必要となる。さらに、モールドを押圧する圧力を過度に高めると、モールド自身が変形してしまい、高精度の転写ができず、最悪の場合、モールドや基板材料に損傷を引き起こす原因ともなる。
すなわち、モールドに形成した凹凸形状を基材表面上に塗布されたレジスト層あるいは供給されたレジストに転写するインプリントを、モールドに形成した凹部にレジスト層が侵入するときの温度及び凹部内の圧力で凝縮する気体の雰囲気中で行う。なお、特許文献1では、この気体の常温での蒸気圧を0.05MPa以上1.00MPa以下としている。
さらに、本発明者らは非特許文献4において、凝縮性ガスであるペンタフルオロプロパン1種類とヘリウムガスを混合させた雰囲気下でナノインプリントすることにより、形成したパターンの表面粗さ、離型力、レジストのモールドへの充填速度を調整できることを報告している。
一般に、微細孔内にある蒸気は、毛細管力により微細孔外にある蒸気に比べて液体になりやすく、この現象を毛管凝縮という。特許文献1に示されるように、飽和蒸気圧の低い凝縮性ガスを用いた場合には、水などに比べて毛管凝縮が起こる可能性が高まる。
特に、最先端半導体の線幅サイズの100nm以下の微細溝のパターンの場合には、飽和蒸気圧が低い凝縮性ガスを用いると、毛管凝縮により、モールドの溝部に光硬化性樹脂が充填される前に、凝縮性ガスが結露してしまい、レジストの充填不良が起こり、結果的に形成パターン不良原因となることがある。
このフォトリソグラフィはあくまで、下地の膜や基材等の対象物をエッチングするためのマスクパターンを形成するものであり、フォトリソグラフィ工程の後には、製膜工程やドライ・ウェット方式のエッチングが行われる。
こうした製膜工程やエッチング工程では、フォトリソグラフィで形成したレジストパターンは、必ず寸法変動を伴うために、通常デバイス試作では、フォトリソグラフィ、製膜、エッチング工程というすべてプロセスフローを繰り返し行い、パターン線幅や形状の最適化に長時間を要している。
すなわち、ナノインプリントをフォトリソグラフィに応用しようとした場合には、モールドの構造を忠実に転写してしまうため、決まった寸法以外、パターン形成することができないという制約がある。
さらに、ナノインプリントのモールドは、電子ビーム描画装置とエッチングにより作製する必要があり、1つのモールドを作製するのに多大の時間とコストを要することとなり、ナノインプリントの導入が製造コストを高める要因ともなっている。
そこで、本発明の目的は、毛管凝縮によるレジストの充填不良を防止するとともに、同一のモールドを用いても、パターン線幅や形状の調整を可能にすることにある。
ここで、毛管凝縮が起こり得る条件下においては、ケルビンの拡張式から、
ただし、
p0:凝縮性ガスの飽和蒸気圧 p:実際の蒸気圧
V:凝縮性ガスの液体のモル体積 m3/mol γ:凝縮性ガスの液体の表面張力N/m
R:気体定数(8.31m2kg/s2Kmol) T:温度293.15K(20℃)
θ:接触角 a:毛細管半径m
とする。
毛管凝縮が起こる毛細管aの半径を求めるため、上式を変形すると、
凝縮性ガスの液体は表面張力が小さく濡れ性が非常に高いため、接触角θを0°と仮定し、これを式(2)に代入することで、毛細管半径a≦10.82nmが求まる。
ホールパターンの直径と考えた場合には2aとなり、21.64nmが求まる。
一方、20℃における飽和蒸気圧が、0.419MPaであるトランス-1,3,3,3-テトラフルオロプロペンの場合には、p:実際の蒸気圧101.3kPa、V: 凝縮性ガスの液体のモル体積101.8×10-6m3/mol、γ: 凝縮性ガスの液体の表面張力0.00855N/m、R:気体定数8.31m2kg/s2Kmol、T:温度293.15K(20℃)、θ:接触角0°とする。
これを式(2)に代入すると、毛細管半径a≦0.50nmとなし、ナノインプリントが適用される5nm~数100nmの半導体パターンの寸法においては、毛管凝縮の影響を受けないことが分かる。
飽和蒸気圧が常温において0.05MPa以上0.2MPa未満の第1凝縮性ガスでは毛管凝縮の生じるホールパターンの直径が10nm以上を示しており、単体のガスでは毛管凝縮の影響を受けてしまうことが分かる。
一方、飽和蒸気圧が常温において0.2MPa以上1MPa以下の第2凝縮性ガスでは、ナノインプリントの応用が期待されているパターン寸法5nm~数100nmにおいては、毛管凝縮の影響を受けない。
さらに、飽和蒸気圧の異なる混合した凝縮ガス雰囲気下を任意に制御することにより、ナノインプリントしたパターンの幅を任意に変更することが可能となり、1つのモールドを作製してしまえば、様々な線幅の転写パターンを作り出すことが可能となる。
具体的には、上記の飽和蒸気圧の異なる第1凝縮性ガスと第2凝縮性ガスを混合した場合における毛管凝縮が生じるパターン寸法を、式(1)の計算に基づいて求めることができる。
両凝縮性ガスを互いに希釈したものとして、分圧に基づいて、第1凝縮性ガスと第2凝縮性ガスの影響を単純加算することで、毛管凝縮の影響度を次の式(3)により近似的に求めることが可能である。
ただし、
p01:第1凝縮性ガスの飽和蒸気圧 p02:第2凝縮性ガスの飽和蒸気圧
p1:第1凝縮性ガスの分圧 p2:第2凝縮性ガスの分圧
V1:第1凝縮性ガスの液体のモル体積m3/mol
V2:第2凝縮性ガスの液体のモル体積m3/mol
γ1:第1凝縮性ガスの液体の表面張力 N/m
γ2:第2凝縮性ガスの液体の表面張力 N/m
θ:接触角 R:気体定数(8.31m2kg/s2Kmol)
T:温度293.15K(20℃) a:毛細管半径m
とする。
このときナノインプリントの応用が期待されているパターン寸法5nm~数100nmにおいては本手法を適用する場合は、毛管凝縮の生じるホールパターンの直径の5nm以下となる第1凝縮性ガスに対する第2凝縮性ガスの割合が35%以上の条件下でナノインプリントを行えばよい。
インプリント装置は、基板1上に溶融状態で成膜された光硬化性樹脂2に対し、微細なパターンが形成されたモールド3を押圧し、両者を接触させた状態で光硬化性樹脂2を硬化させることによって、基板1上にパターンを転写する。
このようなインプリント装置は、例えば、半導体デバイス、マイクロセンサを製造するために用いられる。
インプリントの転写方式として、基板とほぼ同じ大きさのパターンを有するモールド3を用いてパターンを一括で転写する方式と、基板よりも小さなパターンを有するモールドを用いて複数回パターンを転写するステップアンドリピート方式、円筒型のモールドを用いて、連続的にパターンを転写するロール型の方式などが挙げられるが、モールドや金型を使用した転写方式であれば、これに限られるものではない。
このように、基板1とモールド3との間で形成される空間に複数の凝縮性ガスを供給する方法は、高濃度の混合ガス環境下を作り出す方法として非常に簡便であるが、チャンバー等、インプリントする空間ごと閉所空間にする方法など、基板1とモールド3との間に混合雰囲気を作り出せる方法であれば、これに限るものではない。
インプリント条件は加圧力0.1MPa、加圧時間10秒間、UV照射強度100mJ/cm2、照射時間1秒間である。第1凝縮性ガスとして、20℃における飽和蒸気圧が、0.107MPaであるトランス-1-クロロ-3,3,3-トリフルオロプロペンを、第2凝縮性ガスとして、20℃における飽和蒸気圧が、0.419MPaであるトランス-1,3,3,3-テトラフルオロプロペンを用いた。
1回目は第1凝縮性ガス100%、第2凝縮性ガス0%、2回目は第1凝縮性ガス75%、第2凝縮性ガス25%、3回目は第1凝縮性ガス50%、第2凝縮性ガス50%、4回目は第1凝縮性ガス25%、第2凝縮性ガス75%、そして、5回目は第1凝縮性ガス0%、第2凝縮性ガス100%とした。
ただし、いずれの場合も、窒素、酸素等の不可避の成分が若干含まれている。
図4のパターンは、直線溝の幅が70nm、溝深さが100nmのモールド構造を、図5のパターンは、直線溝の幅が125nm、溝深さが100nmのモールド構造を転写したものである。それぞれ、気泡欠陥などのパターン不良は見られずに、良好にパターン形成がなされている。
第2凝縮性ガスの割合が0%(第1凝縮性ガスが100%)のときに、インプリントしたパターンの線幅が最も小さく、反対に、第2凝縮性ガスが100%(第1凝縮性ガスが0%)のときに、インプリントしたパターンの線幅が最も大きかった。
図7に第1と第2の凝縮ガスの混合条件を変えた雰囲気下での、直線溝の幅が125nm、溝深さが100nmのモールド構造を転写したパターンの線幅のグラフを示す。上述と同様に第2のガスの割合に依存して直線性の高い線幅の変動を確認することができた。
2:光硬化性樹脂
3:モールド
4a、4b:ノズル
5:凝縮性ガス供給管
6:第1凝縮性ガスタンク
7:第2凝縮性ガスタンク
6a、7a:調整バルブ
Claims (3)
- モールドに形成した凹部にレジスト層が侵入し、前記レジスト層で封止された前記凹部内部の温度、圧力で凝縮する凝縮性ガスの雰囲気中で、前記モールドに形成した凹部の転写を行うインプリント装置において、
前記凝縮性ガスとして、飽和蒸気圧の異なる複数の凝縮性ガスを一定の比率で供給する供給装置を備えたことを特徴とするインプリント装置。 - 前記飽和蒸気圧の異なる複数の凝縮性ガスは、飽和蒸気圧が常温において0.05MPa以上0.2MPa未満の第1凝縮性ガスと、飽和蒸気圧が常温において0.2MPa以上1MPa以下の第2凝縮性ガスを含むことを特徴とする請求項1に記載されたインプリント装置。
- 前記第1凝縮性ガスは、少なくともトランス-1-クロロ-3,3,3-トリフルオロプロペンを含むものであり、前記第2凝縮性ガスは、少なくとも、トランス-1,3,3,3-テトラフルオロプロペン、または、2,3,3,3-テトラフルオロ-1-プロペンを含むものであることを特徴とする請求項2に記載されたインプリント装置。
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