公开(公告)号：US11823897B2

公开(公告)日：2023-11-21

申请号：US17697311

申请日：2022-03-17

Applicant: TOKYO ELECTRON LIMITED

Inventor： Makoto Muramatsu ,  Hisashi Genjima

IPC: C23C18/14 ,  H01L21/02

CPC classification number: H01L21/02348 ,  C23C18/143 ,  H01L21/0214 ,  H01L21/02164 ,  H01L21/02222 ,  H01L21/02282 ,  H01L21/02323 ,  H01L21/02326

Abstract: There is provided a technique of forming an insulating film containing silicon oxide. A coating solution containing polysilazane is applied onto a wafer W, the solvent of the coating solution is volatilized, and the coating film is irradiated with ultraviolet rays in nitrogen atmosphere before performing a curing process. Dangling bonds are generated in silicon which is a pre-hydrolyzed site in polysilazane. Therefore, the energy for hydrolysis is reduced, and unhydrolyzed sites are reduced even when the temperature of the curing process is 350° C. Since efficient dehydration condensation occurs, the crosslinking rate is improved, and a dense (good-quality) insulation film is formed. By forming a protective film on the surface of the coating film to which ultraviolet rays irradiated, the reaction of dangling bonds prior to the curing process is suppressed.

公开(公告)号：US11315784B2

公开(公告)日：2022-04-26

申请号：US16645712

申请日：2018-08-28

Applicant: TOKYO ELECTRON LIMITED

Inventor： Makoto Muramatsu ,  Hisashi Genjima

IPC: H01L21/02 ,  C23C18/14

Abstract: There is provided a technique of forming an insulating film containing silicon oxide. A coating solution containing polysilazane is applied onto a wafer W, the solvent of the coating solution is volatilized, and the coating film is irradiated with ultraviolet rays in nitrogen atmosphere before performing a curing process. Dangling bonds are generated in silicon which is a pre-hydrolyzed site in polysilazane. Therefore, the energy for hydrolysis is reduced, and unhydrolyzed sites are reduced even when the temperature of the curing process is 350° C. Since efficient dehydration condensation occurs, the crosslinking rate is improved, and a dense (good-quality) insulation film is formed. By forming a protective film on the surface of the coating film to which ultraviolet rays irradiated, the reaction of dangling bonds prior to the curing process is suppressed.

公开(公告)号：US10418242B2

公开(公告)日：2019-09-17

申请号：US15512614

申请日：2015-09-15

Applicant: Tokyo Electron Limited

Inventor： Makoto Muramatsu ,  Tadatoshi Tomita ,  Hisashi Genjima ,  Gen You ,  Takahiro Kitano

IPC: H01L21/027 ,  H01L21/033 ,  G03F7/40 ,  H01L21/31 ,  C08J7/18 ,  D06M14/18 ,  G03D5/00 ,  H01L21/02 ,  H01L21/67 ,  H01L29/51 ,  H01L29/66 ,  G03F7/00 ,  H01J37/32 ,  H05H1/46

Abstract: A substrate treatment method of treating a substrate using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer, includes: a resist pattern formation step of forming a predetermined resist pattern by a resist film on the substrate; a thin film formation step of forming a thin film for suppressing deformation of the resist pattern on a surface of the resist pattern; a block copolymer coating step of applying a block copolymer to the substrate after the formation of the thin film; and a polymer separation step of phase-separating the block copolymer into the hydrophilic polymer and the hydrophobic polymer.

公开(公告)号：US11574812B2

公开(公告)日：2023-02-07

申请号：US16516344

申请日：2019-07-19

Applicant: Tokyo Electron Limited

Inventor： Makoto Muramatsu ,  Tadatoshi Tomita ,  Hisashi Genjima ,  Gen You ,  Takahiro Kitano

IPC: H01L21/027 ,  H01L21/033 ,  G03F7/00 ,  G03F7/40 ,  H01L21/31 ,  H01L21/67 ,  H05H1/46

Abstract: A substrate treatment method of treating a substrate using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer, includes: a resist pattern formation step of forming a predetermined resist pattern by a resist film on the substrate; a thin film formation step of forming a thin film for suppressing deformation of the resist pattern on a surface of the resist pattern; a block copolymer coating step of applying a block copolymer to the substrate after the formation of the thin film; and a polymer separation step of phase-separating the block copolymer into the hydrophilic polymer and the hydrophobic polymer.

公开(公告)号：US20220208547A1

公开(公告)日：2022-06-30

申请号：US17697311

申请日：2022-03-17

Applicant: TOKYO ELECTRON LIMITED

Inventor： Makoto Muramatsu ,  Hisashi Genjima

IPC: H01L21/02 ,  C23C18/14

Abstract: There is provided a technique of forming an insulating film containing silicon oxide. A coating solution containing polysilazane is applied onto a wafer W, the solvent of the coating solution is volatilized, and the coating film is irradiated with ultraviolet rays in nitrogen atmosphere before performing a curing process. Dangling bonds are generated in silicon which is a pre-hydrolyzed site in polysilazane. Therefore, the energy for hydrolysis is reduced, and unhydrolyzed sites are reduced even when the temperature of the curing process is 350° C. Since efficient dehydration condensation occurs, the crosslinking rate is improved, and a dense (good-quality) insulation film is formed. By forming a protective film on the surface of the coating film to which ultraviolet rays irradiated, the reaction of dangling bonds prior to the curing process is suppressed.

公开(公告)号：US10329144B2

公开(公告)日：2019-06-25

申请号：US15554026

申请日：2016-02-10

Applicant: Tokyo Electron Limited

Inventor： Makoto Muramatsu ,  Tadatoshi Tomita ,  Hisashi Genjima ,  Gen You ,  Takahiro Kitano ,  Takanori Nishi

IPC: C03C15/00 ,  B81C1/00 ,  B82Y40/00 ,  C08F297/00 ,  H01L21/027 ,  H01L21/033 ,  H01L21/67 ,  H01L21/677

Abstract: A substrate treatment method using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer includes a polymer separating step, wherein a ratio of a molecular weight of the hydrophilic polymer in the block copolymer is adjusted to 20% to 40% so that the hydrophilic polymers align at positions corresponding to a hexagonal close-packed structure in a plan view after the polymer separating step, and at the polymer separating step, a columnar first hydrophilic polymer is phase-separated on each of circular patterns of hydrophobic coating films and a columnar second hydrophilic polymer is phase-separated between the first hydrophilic polymers, and a diameter of the circular pattern is set so that the first hydrophilic polymers and the second hydrophilic polymers align at positions corresponding to the hexagonal close-packed structure in a plan view.

公开(公告)号：US11631581B2

公开(公告)日：2023-04-18

申请号：US16604744

申请日：2018-03-13

Applicant: TOKYO ELECTRON LIMITED

Inventor： Makoto Muramatsu ,  Yusuke Saito ,  Hisashi Genjima ,  Hiroyuki Fujii

IPC: H01L21/324 ,  H01L21/02 ,  B05D3/06

Abstract: A technique for obtaining good film quality in forming a silicon-oxide-containing insulating film as a coating film on a substrate. A coating liquid containing polysilazane is applied to a wafer, a solvent in the coating liquid is volatilized, and then the coating film is irradiated with ultraviolet rays under a nitrogen atmosphere before performing a curing process. Thus, dangling bonds are likely to be formed at hydrolyzed portions in polysilazane. Since dangling bonds are formed in advance at portions in silicon to be hydrolyzed, productivity of hydroxyl groups is enhanced. That is, since an energy required for hydrolysis is reduced, the number of the portions remaining without being hydrolyzed is reduced even when the curing process is performed at a low temperature. Therefore, dehydration synthesis occurs efficiently, which increases a crosslinking rate and makes it possible to form a dense (good film quality) insulating film.

公开(公告)号：US10586711B2

公开(公告)日：2020-03-10

申请号：US15763529

申请日：2016-10-20

Applicant: Tokyo Electron Limited

Inventor： Makoto Muramatsu ,  Tadatoshi Tomita ,  Hisashi Genjima ,  Takahiro Kitano

IPC: H01L21/311 ,  G03F7/16 ,  G03F7/20 ,  G03F7/30 ,  G03F7/38 ,  G03F7/42 ,  H01L21/027 ,  H01L21/67

Abstract: A substrate processing method of processing a substrate using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer, the substrate processing method includes: a block copolymer coating step of applying the block copolymer onto the substrate on which a predetermined projecting and recessed pattern is formed, to form a coating film of the block copolymer; a polymer separation step of phase-separating the block copolymer into the hydrophilic polymer and the hydrophobic polymer; a polymer removal step of selectively removing the hydrophilic polymer from the phase-separated block copolymer; and after the block copolymer coating step and before the polymer removal step, a film thickness reduction step of reducing a film thickness of the coating film of the block copolymer.

公开(公告)号：US09418860B2

公开(公告)日：2016-08-16

申请号：US14518699

申请日：2014-10-20

Applicant: Tokyo Electron Limited

Inventor： Mark H. Somervell ,  Makoto Muramatsu ,  Benjamen M. Rathsack ,  Tadatoshi Tomita ,  Hisashi Genjima ,  Hidetami Yaegashi ,  Kenichi Oyama

IPC: H01L21/302 ,  H01L21/308 ,  G03F7/42 ,  H01L21/027 ,  G03F7/00 ,  G03F7/09 ,  H01L21/033 ,  H01L21/3213

CPC classification number: G03F7/0002 ,  G03F7/091 ,  G03F7/165 ,  G03F7/40 ,  G03F7/42 ,  H01L21/0273 ,  H01L21/0335 ,  H01L21/0337 ,  H01L21/0338 ,  H01L21/3081 ,  H01L21/3086 ,  H01L21/3088 ,  H01L21/31116 ,  H01L21/32139

Abstract: A method is provided for forming a patterned topography on a substrate. The substrate is provided with features formed atop that constitute an existing topography, and a template for directed self-assembly (DSA) is formed surrounding the exposed topography. Further to the method, the exposed template surfaces are chemically treated. In one embodiment, the surfaces are treated with a hydrogen-containing reducing chemistry to alter the surfaces to a less oxidized state. In another embodiment, the surfaces are coated with a first phase of a block copolymer (BCP) to render the surfaces more attractive to the first phase than prior to the coating. The template is then filled with the BCP to cover the exposed topography, and then the BCP is annealed within the template to drive self-assembly in alignment with the topography. Developing the annealed BCP exposes a DSA pattern immediately overlying the topography.

Abstract translation: 提供了一种在衬底上形成图案形貌的方法。 衬底具有形成在顶部的构成现有形貌的特征，并且围绕暴露的形貌形成用于定向自组装（DSA）的模板。 除了该方法之外，曝光的模板表面经化学处理。 在一个实施方案中，用含氢还原化学处理表面以将表面改变为较少氧化的状态。 在另一个实施方案中，表面涂覆有嵌段共聚物（BCP）的第一相，使表面比涂覆前比第一相更有吸引力。 然后用BCP填充模板以覆盖暴露的形貌，然后在模板内对BCP进行退火以驱动与地形对准的自组装。 开发退火的BCP暴露了立即覆盖地形的DSA模式。

公开(公告)号：US20150111387A1

公开(公告)日：2015-04-23

申请号：US14518699

申请日：2014-10-20

Applicant: Tokyo Electron Limited

Inventor： Mark H. Somervell ,  Makoto Muramatsu ,  Benjamen M. Rathsack ,  Tadatoshi Tomita ,  Hisashi Genjima ,  Hidetami Yaegashi ,  Kenichi Oyama

IPC: H01L21/308 ,  H01L21/027

CPC classification number: G03F7/0002 ,  G03F7/091 ,  G03F7/165 ,  G03F7/40 ,  G03F7/42 ,  H01L21/0273 ,  H01L21/0335 ,  H01L21/0337 ,  H01L21/0338 ,  H01L21/3081 ,  H01L21/3086 ,  H01L21/3088 ,  H01L21/31116 ,  H01L21/32139

Abstract: A method is provided for forming a patterned topography on a substrate. The substrate is provided with features formed atop that constitute an existing topography, and a template for directed self-assembly (DSA) is formed surrounding the exposed topography. Further to the method, the exposed template surfaces are chemically treated. In one embodiment, the surfaces are treated with a hydrogen-containing reducing chemistry to alter the surfaces to a less oxidized state. In another embodiment, the surfaces are coated with a first phase of a block copolymer (BCP) to render the surfaces more attractive to the first phase than prior to the coating. The template is then filled with the BCP to cover the exposed topography, and then the BCP is annealed within the template to drive self-assembly in alignment with the topography. Developing the annealed BCP exposes a DSA pattern immediately overlying the topography.

Abstract translation: 提供了一种在衬底上形成图案形貌的方法。 衬底具有形成在顶部的构成现有形貌的特征，并且围绕暴露的形貌形成用于定向自组装（DSA）的模板。 除了该方法之外，曝光的模板表面经化学处理。 在一个实施方案中，用含氢还原化学处理表面以将表面改变为较少氧化的状态。 在另一个实施方案中，表面涂覆有嵌段共聚物（BCP）的第一相，使表面比涂覆前比第一相更有吸引力。 然后用BCP填充模板以覆盖暴露的形貌，然后在模板内对BCP进行退火以驱动与地形对准的自组装。 开发退火的BCP暴露了立即覆盖地形的DSA模式。