JPWO2019150548A1 - Semiconductor impurity liquid source, method of manufacturing semiconductor impurity liquid source, and method of manufacturing semiconductor device - Google Patents
Semiconductor impurity liquid source, method of manufacturing semiconductor impurity liquid source, and method of manufacturing semiconductor device Download PDFInfo
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- H—ELECTRICITY
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
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- H—ELECTRICITY
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/228—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a liquid phase, e.g. alloy diffusion processes
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/24—Alloying of impurity materials, e.g. doping materials, electrode materials, with a semiconductor body
Abstract
不純物を含む化合物、化合物を溶解する有機溶剤、有機溶剤に溶解し液体ソースに粘性を付与する増粘剤、不純物より大きい直径の無機粉末が含有され、増粘剤は、液体ソースを半導体基板の塗布面に塗布する際、粘性によって隣り合う無機粉末同士の間隔を調整して塗布面上への不純物の分布を調整し、第１の温度に加熱されて隣り合う無機粉末同士の間に析出して不純物の分布を維持し、無機粉末は、半導体基板同士の間隔の分布を調整し、不純物を第２の温度に加熱後、接合された半導体基板を剥離液に晒す際に、半導体基板同士の間隔を維持していることで半導体基板間に剥離液を浸透させる。It contains a compound containing impurities, an organic solvent that dissolves the compound, a thickener that dissolves in the organic solvent and gives viscosity to the liquid source, and an inorganic powder having a diameter larger than that of the impurity. When applying to the application surface, the spacing between adjacent inorganic powders is adjusted by viscosity to adjust the distribution of impurities on the application surface, and heated to a first temperature to precipitate between adjacent inorganic powders. After maintaining the distribution of the impurities, the inorganic powder adjusts the distribution of the spacing between the semiconductor substrates, heats the impurities to the second temperature, and then exposes the bonded semiconductor substrates to a stripping solution. By maintaining the interval, the stripping liquid permeates between the semiconductor substrates.
Description
本発明は、半導体不純物液体ソース、半導体不純物液体ソースの製造方法および半導体装置の製造方法に関する。 The present invention relates to a semiconductor impurity liquid source, a method for manufacturing a semiconductor impurity liquid source, and a method for manufacturing a semiconductor device.
従来から、半導体プロセスでは、塗布コータヘッド上に載置されたＳｉウェーハを塗布コータヘッドで回転させながら、ノズルによって上方からＳｉウェーハに不純物の液体ソースを滴下することが行われていた。Ｓｉウェーハに滴下された液体ソースは、回転するＳｉウェーハの遠心力によってＳｉウェーハに全面的に塗布される。そして、液体ソースが塗布されたＳｉウェーハを加熱することで、Ｓｉウェーハに不純物を熱拡散することができる。また、一度に大量のＳｉウェーハを処理するため、不純物の熱拡散においては、液体ソースが塗布された複数枚のＳｉウェーハを積層し、積層されたＳｉウェーハをまとめて加熱することで、複数枚のＳｉウェーハに同時に熱拡散を行っていた。そして、熱拡散が完了した後は、フッ酸中にＳｉウェーハの積層体を浸漬することで、積層体から単体毎にＳｉウェーハを剥離する。 2. Description of the Related Art Conventionally, in a semiconductor process, a liquid source of an impurity is dropped on a Si wafer from above by a nozzle while rotating the Si wafer placed on the coating coater head by the coating coater head. The liquid source dropped on the Si wafer is entirely applied to the Si wafer by the centrifugal force of the rotating Si wafer. Then, by heating the Si wafer to which the liquid source is applied, impurities can be thermally diffused into the Si wafer. In addition, in order to process a large number of Si wafers at once, in thermal diffusion of impurities, a plurality of Si wafers coated with a liquid source are stacked, and the stacked Si wafers are heated together to form a plurality of Si wafers. At the same time. After completion of the thermal diffusion, the Si wafer laminate is immersed in hydrofluoric acid to separate the Si wafer from the laminate for each single body.
しかしながら、従来は、不純物の拡散の均一性を確保しつつ半導体基板の剥離の所要時間を短縮して半導体装置の製造効率を向上させることについて、有効な提案がなされていなかった。 However, conventionally, no effective proposal has been made to improve the manufacturing efficiency of a semiconductor device by shortening the time required for peeling a semiconductor substrate while ensuring uniformity of impurity diffusion.
例えば、特開平１１−１７６７６４号公報には、不純物の化合物および有機系バインダを含む拡散用フィルムが開示されているが、この技術では、有機系バインダが不純物の拡散の均一性に何ら寄与することができず、また、フィルムを溶融させる工程が必要であるため製造効率を向上させることもできない。したがって、特開平１１−１７６７６４号公報に記載の技術は、本発明とは全く異なる技術である。 For example, Japanese Patent Application Laid-Open No. H11-176664 discloses a diffusion film containing a compound of an impurity and an organic binder. In this technique, however, the organic binder does not contribute to the uniformity of diffusion of the impurity. In addition, the production efficiency cannot be improved because a step of melting the film is required. Therefore, the technology described in Japanese Patent Application Laid-Open No. 11-176664 is a technology completely different from the present invention.
そこで、本発明は、不純物の拡散の均一性を確保しつつ半導体基板の剥離の所要時間を短縮して半導体装置の製造効率を向上させることができる半導体不純物液体ソース、半導体不純物液体ソースの製造方法および半導体製造方法を提供することを目的とする。 Accordingly, the present invention provides a semiconductor impurity liquid source and a method for manufacturing a semiconductor impurity liquid source, which can shorten the time required for peeling a semiconductor substrate and improve the manufacturing efficiency of a semiconductor device while ensuring uniformity of impurity diffusion. And a semiconductor manufacturing method.
本発明の一態様に係る半導体不純物液体ソースは、
積層された複数の半導体基板間に塗布された状態で加熱されることで、前記複数の半導体基板に不純物を拡散させる半導体不純物液体ソースであって、
前記不純物を含む化合物と、
前記化合物を溶解する有機溶剤と、
前記有機溶剤に溶解し、前記半導体不純物液体ソースに粘性を付与する増粘剤と、
前記不純物よりも大きい直径を有する無機粉末と、が混合して含有され、
前記増粘剤は、
前記半導体不純物液体ソースを前記半導体基板の塗布面に塗布する際に、前記半導体不純物液体ソースに付与する前記粘性によって、前記塗布面に沿った面方向において隣り合う前記無機粉末同士の間隔を調整して前記塗布面上への前記不純物の分布を調整し、
前記半導体不純物液体ソースを乾燥させる第１の温度に加熱されることで、前記有機溶剤の蒸発にともなって前記隣り合う無機粉末同士の間に析出して前記塗布面上への前記不純物の分布を維持する特性を有し、
前記無機粉末は、
前記複数の半導体基板を積層する際に、前記増粘剤によって前記面方向において隣り合う無機粉末同士の間隔が調整されていることで、前記複数の半導体基板同士の間隔の前記面方向における分布を調整し、
前記不純物を前記第１の温度よりも高い温度である前記不純物の拡散供給源が生成される第２の温度に加熱した後、前記第２の温度での加熱によって接合された前記複数の半導体基板を剥離液に晒す際に、前記複数の半導体基板同士の間隔を維持していることで、前記複数の半導体基板間に前記剥離液を浸透させる特性を有する。The semiconductor impurity liquid source according to one embodiment of the present invention includes:
A semiconductor impurity liquid source that diffuses impurities into the plurality of semiconductor substrates by being heated while being applied between the plurality of stacked semiconductor substrates,
A compound containing the impurity,
An organic solvent that dissolves the compound,
A thickener that is dissolved in the organic solvent and imparts viscosity to the semiconductor impurity liquid source,
And an inorganic powder having a diameter larger than the impurities,
The thickener is
When applying the semiconductor impurity liquid source to the application surface of the semiconductor substrate, the viscosity provided to the semiconductor impurity liquid source adjusts a distance between the inorganic powders adjacent in a surface direction along the application surface. Adjusting the distribution of the impurities on the coating surface,
By being heated to a first temperature for drying the semiconductor impurity liquid source, with the evaporation of the organic solvent, it is deposited between the adjacent inorganic powders and the distribution of the impurity on the application surface is reduced. Has the property of maintaining,
The inorganic powder,
When laminating the plurality of semiconductor substrates, by adjusting the interval between the inorganic powder adjacent in the surface direction by the thickener, the distribution of the interval between the plurality of semiconductor substrates in the surface direction. Adjust,
The plurality of semiconductor substrates joined by heating the impurity to a second temperature, which is higher than the first temperature, at which the impurity diffusion supply source is generated, and then heating the impurity at the second temperature When exposing the semiconductor substrate to the stripping liquid, the gap between the plurality of semiconductor substrates is maintained, so that the stripping liquid permeates between the plurality of semiconductor substrates.
また、前記半導体不純物液体ソースにおいて、
前記半導体不純物液体ソース全体に対する前記無機粉末の質量濃度は、前記半導体不純物液体ソース全体に対する前記増粘剤の質量濃度よりも低くてもよい。Further, in the semiconductor impurity liquid source,
The mass concentration of the inorganic powder with respect to the entire semiconductor impurity liquid source may be lower than the mass concentration of the thickener with respect to the entire semiconductor impurity liquid source.
また、前記半導体不純物液体ソースにおいて、
前記半導体不純物液体ソース全体に対する前記無機粉末の質量濃度は、前記半導体不純物液体ソース全体に対する前記有機溶剤の質量濃度よりも低くてもよい。Further, in the semiconductor impurity liquid source,
The mass concentration of the inorganic powder with respect to the entire semiconductor impurity liquid source may be lower than the mass concentration of the organic solvent with respect to the entire semiconductor impurity liquid source.
また、前記半導体不純物液体ソースにおいて、
前記剥離液は、フッ酸であってもよい。Further, in the semiconductor impurity liquid source,
The stripping solution may be hydrofluoric acid.
また、前記半導体不純物液体ソースにおいて、
前記無機粉末は、主成分として、Ｓｉ、ＳｉＯ２、ＳｉＣおよびＳｉ３Ｎ４からなる群から選択される少なくとも１つの物質を含有してもよい。Further, in the semiconductor impurity liquid source,
The inorganic powder may contain, as a main component, at least one substance selected from the group consisting of Si, SiO 2 , SiC, and Si 3 N 4 .
また、前記半導体不純物液体ソースにおいて、
前記増粘剤は、主成分として、セルロースまたはその誘導体を含有してもよい。Further, in the semiconductor impurity liquid source,
The thickener may contain cellulose or a derivative thereof as a main component.
また、前記半導体不純物液体ソースにおいて、
前記増粘剤は、主成分として、ヒドロキシプロピルセルロースを含有してもよい。Further, in the semiconductor impurity liquid source,
The thickener may contain hydroxypropyl cellulose as a main component.
また、前記半導体不純物液体ソースにおいて、
前記有機溶剤は、主成分として、エタノール、アセトン、又はプロパノールを含有してもよい。Further, in the semiconductor impurity liquid source,
The organic solvent may contain ethanol, acetone, or propanol as a main component.
また、前記半導体不純物液体ソースにおいて、
前記化合物は、ほう酸および乳酸アルミニウムであってもよい。Further, in the semiconductor impurity liquid source,
The compound may be boric acid and aluminum lactate.
また、前記半導体不純物液体ソースにおいて、
前記化合物は、ピロりん酸であってもよい。Further, in the semiconductor impurity liquid source,
The compound may be pyrophosphate.
また、前記半導体不純物液体ソースにおいて、
更に、水を含有してもよい。Further, in the semiconductor impurity liquid source,
Further, water may be contained.
本発明の一態様に係る半導体不純物液体ソースの製造方法は、
前記不純物を含む化合物と、前記化合物を溶解する有機溶剤と、前記有機溶剤に溶解し、前記半導体不純物液体ソースに粘性を付与する増粘剤と、を混合した混合液を生成する工程と、
前記混合液の粘性を安定させるために前記混合液を予め決められた時間所定の雰囲気下で保持する工程と、
前記保持の後に、前記混合液に、前記不純物よりも大きい直径を有する無機粉末を混合する工程と、を備える。A method for manufacturing a semiconductor impurity liquid source according to one embodiment of the present invention,
A step of producing a mixed solution of a compound containing the impurity, an organic solvent for dissolving the compound, and a thickener that dissolves in the organic solvent and imparts viscosity to the semiconductor impurity liquid source,
A step of maintaining the mixture under a predetermined atmosphere for a predetermined time to stabilize the viscosity of the mixture,
Mixing the mixed liquid with an inorganic powder having a diameter larger than the impurities after the holding.
前記半導体不純物ソースの製造方法において、
前記保持の前に前記混合液を撹拌する工程を更に備えてもよい。In the method for manufacturing a semiconductor impurity source,
The method may further include a step of stirring the mixture before the holding.
本発明の一態様に係る半導体装置の製造方法は、
複数の半導体基板に、請求項１に記載の半導体不純物液体ソースを塗布する工程と、
前記塗布された半導体不純物液体ソースを第１の温度に加熱することで、前記塗布された半導体不純物液体ソースを乾燥させる工程と、
前記複数の半導体基板を積層させる工程と、
前記複数の半導体基板を積層させる際に、前記無機粉末によって前記複数の半導体基板同士の間隔の分布を調整する工程と、
前記不純物を第２の温度に加熱することで、前記不純物の拡散供給源を生成する工程と、 前記複数の半導体基板を剥離液に浸漬させて、前記第２の温度での加熱によって接合された前記複数の半導体基板同士を剥離する工程と、を備える。A method for manufacturing a semiconductor device according to one embodiment of the present invention includes:
Applying a semiconductor impurity liquid source according to claim 1 to a plurality of semiconductor substrates;
Drying the applied semiconductor impurity liquid source by heating the applied semiconductor impurity liquid source to a first temperature;
Laminating the plurality of semiconductor substrates,
When stacking the plurality of semiconductor substrates, adjusting the distribution of the spacing between the plurality of semiconductor substrates by the inorganic powder,
A step of generating a diffusion supply source of the impurity by heating the impurity to a second temperature; and immersing the plurality of semiconductor substrates in a stripping solution, and joining the semiconductor substrates by heating at the second temperature. Separating the plurality of semiconductor substrates from each other.
本発明の一態様に係る半導体不純物液体ソースは、積層された複数の半導体基板間に塗布された状態で加熱されることで、複数の半導体基板に不純物を拡散させる半導体不純物液体ソースであって、不純物を含む化合物と、化合物を溶解する有機溶剤と、有機溶剤に溶解し、半導体不純物液体ソースに粘性を付与する増粘剤と、不純物よりも大きい直径を有する無機粉末と、が混合して含有され、増粘剤は、半導体不純物液体ソースを半導体基板の塗布面に塗布する際に、半導体不純物液体ソースに付与する粘性によって、塗布面に沿った面方向において隣り合う無機粉末同士の間隔を調整して塗布面上への不純物の分布を調整し、半導体不純物液体ソースを乾燥させる第１の温度に加熱されることで、有機溶剤の蒸発にともなって隣り合う無機粉末同士の間に析出して塗布面上への不純物の分布を維持する特性を有し、無機粉末は、複数の半導体基板を積層する際に、増粘剤によって面方向において隣り合う無機粉末同士の間隔が調整されていることで、複数の半導体基板同士の間隔の面方向における分布を調整し、不純物を第１の温度よりも高い温度である不純物の拡散供給源が生成される第２の温度に加熱した後、第２の温度での加熱によって接合された複数の半導体基板を剥離液に晒す際に、複数の半導体基板同士の間隔を維持していることで、複数の半導体基板間に剥離液を浸透させる特性を有する。 The semiconductor impurity liquid source according to one embodiment of the present invention is a semiconductor impurity liquid source that diffuses impurities into a plurality of semiconductor substrates by being heated while being applied between a plurality of stacked semiconductor substrates, A compound containing impurities, an organic solvent that dissolves the compound, a thickener that dissolves in the organic solvent and imparts viscosity to the semiconductor impurity liquid source, and an inorganic powder having a diameter larger than that of the impurities are mixed and contained. The thickener adjusts the distance between adjacent inorganic powders in the surface direction along the application surface by the viscosity imparted to the semiconductor impurity liquid source when applying the semiconductor impurity liquid source to the application surface of the semiconductor substrate. The semiconductor impurity liquid source is heated to a first temperature for drying the semiconductor impurity liquid source by adjusting the distribution of the impurities on the coating surface, so that the semiconductor solvent liquid sources are adjacent to each other as the organic solvent evaporates. It has the property of maintaining the distribution of impurities on the application surface by being deposited between the machine powders, and the inorganic powder, when laminating a plurality of semiconductor substrates, the inorganic powder adjacent in the surface direction by the thickener By adjusting the spacing between the plurality of semiconductor substrates, the distribution of the spacing between the plurality of semiconductor substrates in the plane direction is adjusted, and a second impurity diffusion source is generated at a temperature higher than the first temperature. When the plurality of semiconductor substrates joined by the heating at the second temperature are exposed to the peeling liquid after heating to the temperature of the second temperature, the interval between the plurality of semiconductor substrates is maintained, so that the It has the property of allowing a stripper to penetrate into
このように、本発明によれば、半導体不純物液体ソースを塗布する際に、増粘剤の粘性によって塗布面上への不純物の分布を調整し、半導体不純物液体ソースを第１の温度で乾燥させる際に、増粘剤が隣り合う無機粉末同士の間に析出して塗布面上への不純物の分布を維持し、複数の半導体基板を積層する際に、増粘剤の粘性で面方向の間隔が調整されている無機粉末によって、半導体基板同士の間隔の面方向における分布を調整し、複数の半導体基板を剥離液に晒す際に、無機粉末で維持された半導体基板同士の間隔を介して剥離液を浸透させることができる。 As described above, according to the present invention, when applying the semiconductor impurity liquid source, the distribution of the impurity on the application surface is adjusted by the viscosity of the thickener, and the semiconductor impurity liquid source is dried at the first temperature. At the time, the thickener precipitates between the adjacent inorganic powders to maintain the distribution of impurities on the application surface, and when laminating a plurality of semiconductor substrates, the viscosity of the thickener increases the spacing in the surface direction. By adjusting the distribution of the spacing between the semiconductor substrates in the plane direction by adjusting the inorganic powder, when exposing a plurality of semiconductor substrates to the stripping solution, the separation is performed via the spacing between the semiconductor substrates maintained by the inorganic powder. The liquid can penetrate.
これにより、不純物の拡散の均一性を確保しつつ半導体基板の剥離の所要時間を短縮して半導体装置の製造効率を向上させることができる。 This makes it possible to shorten the time required for peeling the semiconductor substrate and improve the manufacturing efficiency of the semiconductor device while ensuring uniformity of impurity diffusion.
以下、図面を参照して本発明に係る実施形態を説明する。なお、以下に示す実施形態は、本発明を限定するものではない。また、実施形態で参照する図面において、同一部分または同様な機能を有する部分には同一の符号または類似の符号を付し、その繰り返しの説明は省略する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. The embodiments described below do not limit the present invention. In the drawings referred to in the embodiments, the same portions or portions having similar functions are denoted by the same or similar reference numerals, and the description thereof will not be repeated.
（半導体不純物液体ソース）
まず、本実施形態に係る半導体不純物液体ソースについて説明する。(Semiconductor impurity liquid source)
First, the semiconductor impurity liquid source according to the present embodiment will be described.
本実施形態に係る半導体不純物液体ソースは、積層された複数の半導体基板間に塗布された状態で加熱されることで、複数の半導体基板に不純物を拡散させるものである。このように、積層状態の複数の半導体基板に不純物を拡散させることで、複数の半導体基板に対して不純物を同時に拡散させることができるので、不純物の拡散を効率的に行うことができる。 The semiconductor impurity liquid source according to the present embodiment diffuses impurities into a plurality of semiconductor substrates by being heated while being applied between a plurality of stacked semiconductor substrates. As described above, by diffusing the impurity into the plurality of semiconductor substrates in a stacked state, the impurity can be simultaneously diffused into the plurality of semiconductor substrates, so that the impurity can be efficiently diffused.
半導体不純物液体ソースは、不純物を含む化合物と、化合物を溶解する有機溶剤と、有機溶剤に溶解し、半導体不純物液体ソースに粘性を付与する増粘剤と、不純物よりも大きい直径を有する無機粉末と、が混合して含有されている。半導体不純物液体ソースは、更に水を含有していてもよい。 The semiconductor impurity liquid source is a compound containing an impurity, an organic solvent that dissolves the compound, a thickener that dissolves in the organic solvent and imparts viscosity to the semiconductor impurity liquid source, and an inorganic powder having a diameter larger than the impurity. , Are mixed and contained. The semiconductor impurity liquid source may further contain water.
半導体基板にＰ型の不純物を拡散させるＰ型の半導体不純物液体ソースの場合、不純物の含む化合物としては、例えば、ほう酸、乳酸アルミニウム等を好適に用いることができる。 In the case of a P-type semiconductor impurity liquid source for diffusing a P-type impurity into a semiconductor substrate, as a compound containing the impurity, for example, boric acid, aluminum lactate, or the like can be preferably used.
半導体基板にＮ型の不純物を拡散させるＮ型の半導体不純物液体ソースの場合、不純物の含む化合物としては、例えば、ピロりん酸等を好適に用いることができる。 In the case of an N-type semiconductor impurity liquid source for diffusing an N-type impurity into a semiconductor substrate, for example, pyrophosphoric acid or the like can be suitably used as a compound containing the impurity.
有機溶剤は、不純物を含む化合物を溶解する特性を有する。このような特性を有する有機溶剤としては、例えば、主成分として、エタノール、アセトン又はプロパノール等を含有する有機溶剤を好適に用いることができる。 Organic solvents have the property of dissolving compounds containing impurities. As the organic solvent having such characteristics, for example, an organic solvent containing ethanol, acetone, propanol, or the like as a main component can be suitably used.
増粘剤は、有機溶剤に溶解し、半導体不純物液体ソースに粘性を付与する特性を有する。また、増粘剤は、半導体不純物液体ソースを半導体基板の塗布面に塗布する際に、半導体不純物液体ソースに付与する粘性によって、塗布面に沿った面方向において隣り合う無機粉末同士の間隔を調整して塗布面上への不純物の分布を調整する特性を有する。さらに、増粘剤は、半導体不純物液体ソースを乾燥させる第１の温度に加熱されることで、有機溶剤の蒸発にともなって隣り合う無機粉末同士の間に析出して塗布面上への不純物の分布を維持する特性を有する。 The thickener has the property of dissolving in an organic solvent and imparting viscosity to the semiconductor impurity liquid source. In addition, when the semiconductor impurity liquid source is applied to the application surface of the semiconductor substrate, the viscosity of the thickener adjusts the distance between the inorganic powders adjacent to each other in the surface direction along the application surface by the viscosity imparted to the semiconductor impurity liquid source. To adjust the distribution of impurities on the coating surface. Further, the thickener is heated to the first temperature for drying the semiconductor impurity liquid source, and is deposited between the adjacent inorganic powders with the evaporation of the organic solvent, and the impurity is deposited on the application surface. It has the property of maintaining distribution.
このような特性を有する増粘剤としては、例えば、主成分として、セルロースまたはその誘導体を含有する増粘剤を好適に用いることができる。増粘剤は、より好ましくは、ヒドロキシプロピルセルロースを含有する。 As the thickener having such properties, for example, a thickener containing cellulose or a derivative thereof as a main component can be suitably used. The thickener more preferably contains hydroxypropylcellulose.
無機粉末は、複数の半導体基板を積層する際に、増粘剤によって面方向において隣り合う無機粉末同士の間隔が調整されていることで、複数の半導体基板同士の間隔の面方向における分布を調整する特性を有する。 When stacking a plurality of semiconductor substrates, the inorganic powder adjusts the distribution of the spacing between the plurality of semiconductor substrates in the plane direction by adjusting the spacing between the inorganic powders adjacent in the plane direction by the thickener. Have the property of
また、無機粉末は、不純物を第１の温度よりも高い温度である不純物の拡散供給源が生成される第２の温度に加熱した後、第２の温度での加熱によって接合された複数の半導体基板を剥離液に晒す際に、複数の半導体基板同士の間隔を維持していることで、複数の半導体基板間に剥離液を浸透させる特性を有する。 Further, the inorganic powder is heated to a second temperature at which an impurity diffusion source is generated, which is higher than the first temperature, and then the plurality of semiconductors are joined by heating at the second temperature. When the substrate is exposed to the stripping solution, the spacing between the plurality of semiconductor substrates is maintained, so that the stripping solution permeates between the plurality of semiconductor substrates.
このような特性を有する無機粉末としては、例えば、主成分として、Ｓｉ、ＳｉＯ２、ＳｉＣおよびＳｉ３Ｎ４からなる群から選択される少なくとも１つの物質を含有する無機粉末を好適に用いることができる。As the inorganic powder having such properties, for example, an inorganic powder containing at least one substance selected from the group consisting of Si, SiO 2 , SiC and Si 3 N 4 as a main component is preferably used. it can.
また、無機粉末を介して接合された半導体基板同士を剥離する特性を有する剥離液としては、例えば、フッ酸等を好適に用いることができる。 Further, as a stripping liquid having a property of separating semiconductor substrates bonded via an inorganic powder, for example, hydrofluoric acid or the like can be suitably used.
（半導体不純物液体ソースの製造方法）
次に、既述した半導体不純物液体ソースを製造するための製造方法について説明する。図１は、本実施形態に係る半導体不純物液体ソースの製造方法を示すフローチャートである。(Method of manufacturing semiconductor impurity liquid source)
Next, a manufacturing method for manufacturing the semiconductor impurity liquid source described above will be described. FIG. 1 is a flowchart illustrating a method for manufacturing a semiconductor impurity liquid source according to the present embodiment.
図１に示すように、先ず、不純物を含む化合物と、化合物を溶解する有機溶剤と、有機溶剤に溶解し、半導体不純物液体ソースに粘性を付与する増粘剤と、を混合した混合液を生成する（ステップＳ１）。 As shown in FIG. 1, first, a mixed solution is prepared by mixing a compound containing an impurity, an organic solvent that dissolves the compound, and a thickener that dissolves in the organic solvent and gives viscosity to the semiconductor impurity liquid source. (Step S1).
図２は、本実施形態に係る半導体不純物液体ソースの製造方法において、Ｐ型の半導体不純物液体ソースの製造方法を説明するための説明図である。 FIG. 2 is an explanatory diagram for explaining a method for manufacturing a P-type semiconductor impurity liquid source in the method for manufacturing a semiconductor impurity liquid source according to the present embodiment.
図２に示すように、Ｐ型の半導体不純物液体ソースの混合液を生成する場合、例えば、粉末の乳酸アルミニウムを水に混合させ、乳酸アルミニウムが水に溶解するまで湯煎することで、乳酸アルミニウム液を生成する。このとき、図２に示すように、撹拌しながら湯煎することで、乳酸アルミニウムの溶解時間を短縮させることができる。乳酸アルミニウムは、有機溶剤よりも水に溶解し易い。溶解し易い水に乳酸アルミニウムを溶解させた後に有機溶剤と混合することで、混合液を適切に生成することができる。 As shown in FIG. 2, when a mixed liquid of a P-type semiconductor impurity liquid source is generated, for example, aluminum lactate powder is mixed with water, and the aluminum lactate solution is immersed in water until the aluminum lactate is dissolved in water. Generate At this time, as shown in FIG. 2, the dissolution time of aluminum lactate can be shortened by immersing in hot water while stirring. Aluminum lactate is more soluble in water than organic solvents. By dissolving aluminum lactate in water that is easy to dissolve and then mixing it with an organic solvent, a mixed solution can be appropriately generated.
また、図２に示すように、粉末のほう酸をエタノールに混合させ、ほう酸がエタノールに溶解するまで湯煎することで、ほう酸液を生成する。このとき、図２に示すように、撹拌しながら湯煎することで、ほう酸の溶解時間を短縮させることができる。 Further, as shown in FIG. 2, boric acid is mixed with powdered boric acid, and the mixture is boiled in water until the boric acid is dissolved in ethanol, thereby producing a boric acid solution. At this time, as shown in FIG. 2, the dissolving time of boric acid can be shortened by boiling with stirring.
そして、図２に示すように、乳酸アルミニウム液と、ほう酸液と、有機溶剤と、増粘剤とを混合することで、混合液を生成する。 Then, as shown in FIG. 2, a mixed liquid is generated by mixing the aluminum lactate liquid, the boric acid liquid, the organic solvent, and the thickener.
図３は、本実施形態に係る半導体不純物液体ソースの製造方法において、Ｎ型の半導体不純物液体ソースの製造方法を説明するための説明図である。 FIG. 3 is an explanatory diagram for explaining a method for manufacturing an N-type semiconductor impurity liquid source in the method for manufacturing a semiconductor impurity liquid source according to the present embodiment.
図３に示すように、Ｎ型の半導体不純物液体ソースの混合液を生成する場合、例えば、ピロりん酸と、有機溶剤と、増粘剤とを混合することで、混合液を生成する。 As shown in FIG. 3, when a mixed liquid of an N-type semiconductor impurity liquid source is generated, for example, a mixed liquid is generated by mixing pyrophosphoric acid, an organic solvent, and a thickener.
混合液を生成した後、図１に示すように、混合液の粘性を安定させるために混合液を予め決められた時間所定の雰囲気下で保持する（ステップＳ２）。 After the mixture is generated, as shown in FIG. 1, the mixture is maintained under a predetermined atmosphere for a predetermined time in order to stabilize the viscosity of the mixture (step S2).
混合液を保持した後、混合液に、不純物よりも大きい直径を有する無機粉末を混合する（ステップＳ３）。以上のようにして、半導体不純物液体ソースを得ることができる。 After holding the mixed liquid, the mixed liquid is mixed with an inorganic powder having a diameter larger than that of the impurities (step S3). As described above, a semiconductor impurity liquid source can be obtained.
（半導体装置の製造方法）
次に、既述した半導体不純物液体ソースを用いた半導体装置の製造方法について説明する。(Method of Manufacturing Semiconductor Device)
Next, a method for manufacturing a semiconductor device using the above-described semiconductor impurity liquid source will be described.
図４は、本実施形態に係る半導体装置の製造方法を示すフローチャートである。図５は、本実施形態に係る半導体装置の製造方法において、滴下工程を示す概略断面図である。 FIG. 4 is a flowchart illustrating the method for manufacturing the semiconductor device according to the present embodiment. FIG. 5 is a schematic cross-sectional view showing a dropping step in the method for manufacturing a semiconductor device according to the present embodiment.
先ず、図４に示すように、半導体基板上に半導体不純物液体ソースを滴下する（ステップＳ１１）。例えば、図５に示すように、塗布コータヘッド３上に半導体基板２を載置し、載置された半導体基板２に対して、上方からノズル４によって半導体基板２の塗布面２ａ上にＰ型半導体不純物液体ソース１−Ｐを滴下する。図５に示すように、Ｐ型半導体不純物液体ソース１−Ｐは、Ｐ型不純物１１−Ｐと、有機溶剤１２と、増粘剤１３と、無機粉末１４とが混合して含有されている。なお、Ｐ型半導体不純物液体ソース１−Ｐは、更に、水やエタノールも含有していてもよい。半導体基板２は、例えば、シリコン単結晶基板である。半導体基板２は、不純物が拡散されていてもよい。 First, as shown in FIG. 4, a semiconductor impurity liquid source is dropped on a semiconductor substrate (step S11). For example, as shown in FIG. 5, a semiconductor substrate 2 is placed on a coating coater head 3, and a P-type semiconductor substrate 2 is placed on a coating surface 2a of the semiconductor substrate 2 by a nozzle 4 from above. The semiconductor impurity liquid source 1-P is dropped. As shown in FIG. 5, the P-type semiconductor impurity liquid source 1-P contains a mixture of a P-type impurity 11-P, an organic solvent 12, a thickener 13, and an inorganic powder 14. The P-type semiconductor impurity liquid source 1-P may further contain water and ethanol. The semiconductor substrate 2 is, for example, a silicon single crystal substrate. The semiconductor substrate 2 may have impurities diffused therein.
半導体不純物液体ソースを滴下した後、図４に示すように、滴下された半導体不純物液体ソースを半導体基板に塗布する（ステップＳ１２）。これにより、半導体基板上に拡散源皮膜を形成する。図６は、本実施形態に係る半導体装置の製造方法において、図５に続く塗布工程を示す概略断面図である。半導体不純物液体ソースを塗布する際には、例えば、図６に示すように、塗布コータヘッド３を回転方向ｒに回転させることで、塗布コータヘッド３上に載置された半導体基板２とともに、半導体基板２の塗布面２ａ上のＰ型半導体不純物液体ソース１−Ｐを回転させる。回転によってＰ型半導体不純物液体ソース１−Ｐに遠心力が作用することで、Ｐ型半導体不純物液体ソース１−Ｐは、塗布面２ａの中心側から周辺側に向かって流動して、塗布面２ａ全体に塗布される。 After the semiconductor impurity liquid source is dropped, as shown in FIG. 4, the dropped semiconductor impurity liquid source is applied to the semiconductor substrate (step S12). Thereby, a diffusion source film is formed on the semiconductor substrate. FIG. 6 is a schematic cross-sectional view showing a coating step following FIG. 5 in the method for manufacturing a semiconductor device according to the present embodiment. At the time of applying the semiconductor impurity liquid source, for example, as shown in FIG. 6, by rotating the coating coater head 3 in the rotation direction r, the semiconductor substrate 2 placed on the coating coater head 3 and the semiconductor substrate 2 are coated. The P-type semiconductor impurity liquid source 1-P on the application surface 2a of the substrate 2 is rotated. Due to the centrifugal force acting on the P-type semiconductor impurity liquid source 1-P by rotation, the P-type semiconductor impurity liquid source 1-P flows from the center side of the application surface 2a to the peripheral side, and the application surface 2a It is applied to the whole.
このとき、増粘剤１３によってＰ型半導体不純物液体ソース１−Ｐに付与されている粘性によって、半導体基板２の周辺側への無機粉末１４の移動速度を調整することができる。これにより、塗布面２ａに沿った面方向ｄにおいて隣り合う無機粉末１４同士の間隔ｉを調整することができる。無機粉末１４同士の間隔ｉを調整することで、塗布面２ａ上へのＰ型不純物１１−Ｐの分布を調整することができる。例えば、隣り合う無機粉末１４同士の間隔ｉを均一に調整することで、塗布面２ａ上へのＰ型不純物１１−Ｐの分布を均一に調整することができる。 At this time, the moving speed of the inorganic powder 14 to the peripheral side of the semiconductor substrate 2 can be adjusted by the viscosity given to the P-type semiconductor impurity liquid source 1-P by the thickener 13. Thereby, the interval i between the inorganic powders 14 adjacent in the surface direction d along the application surface 2a can be adjusted. By adjusting the interval i between the inorganic powders 14, the distribution of the P-type impurities 11-P on the application surface 2a can be adjusted. For example, by uniformly adjusting the distance i between the adjacent inorganic powders 14, the distribution of the P-type impurity 11-P on the application surface 2a can be uniformly adjusted.
半導体不純物液体ソースを塗布した後、図４に示すように、半導体基板に塗布された半導体不純物液体ソースを乾燥させる（ステップＳ１３）。図７は、本実施形態に係る半導体装置の製造方法において、図６に続く乾燥工程を示す概略断面図である。半導体不純物液体ソースを乾燥する際には、例えば、図７に示すように、発熱体が内蔵されたベーク板５上に、Ｐ型半導体不純物液体ソース１−Ｐが塗布された半導体基板２を載置し、ベーク板５を乾燥温度（第１の温度）まで加熱する。これにより、有機溶剤および水は概ね蒸発する。一方、図７に示すように、増粘剤１３は、析出（すなわち、固化）して残存している。増粘剤１３が析出していることで、隣り合う無機粉末１４間の間隔ｉを増粘剤１３によって安定的に維持することができる。これにより、塗布面２ａ上へのＰ型不純物１１−Ｐの分布を維持することができる。 After the application of the semiconductor impurity liquid source, the semiconductor impurity liquid source applied to the semiconductor substrate is dried as shown in FIG. 4 (step S13). FIG. 7 is a schematic cross-sectional view showing a drying step following FIG. 6 in the method for manufacturing a semiconductor device according to the present embodiment. When the semiconductor impurity liquid source is dried, for example, as shown in FIG. 7, the semiconductor substrate 2 on which the P-type semiconductor impurity liquid source 1-P is applied is placed on a bake plate 5 having a built-in heating element. Then, the bake plate 5 is heated to the drying temperature (first temperature). Thereby, the organic solvent and water evaporate substantially. On the other hand, as shown in FIG. 7, the thickener 13 is deposited (that is, solidified) and remains. Since the thickener 13 is precipitated, the interval i between the adjacent inorganic powders 14 can be stably maintained by the thickener 13. Thereby, the distribution of the P-type impurity 11-P on the application surface 2a can be maintained.
半導体不純物液体ソースを乾燥させた後、同様の工程（ステップＳ１１〜Ｓ１３）を、半導体基板２の塗布面２ａの反対側の表面を新たな塗布面として、不純物の導電型が異なる半導体不純物液体ソースを用いて行う。 After the semiconductor impurity liquid source is dried, a similar process (steps S11 to S13) is performed by using the surface opposite to the application surface 2a of the semiconductor substrate 2 as a new application surface and using a semiconductor impurity liquid source having a different impurity conductivity type. This is performed using
半導体基板の表裏の塗布面の半導体不純物液体ソースを乾燥させた後、図４に示すように、複数の半導体基板を積層する（ステップＳ１４）。図８は、本実施形態に係る半導体装置の製造方法において、図７に続く積層工程を示す概略断面図である。半導体基板を積層する際には、例えば、図８に示すように、複数の半導体基板２を、同じ導電型の半導体不純物液体ソースの塗布面同士を向かい合わせるように積層させる。なお、図８において、符号１１−Ｎは、Ｎ型不純物である。 After the semiconductor impurity liquid sources on the front and back application surfaces of the semiconductor substrate are dried, a plurality of semiconductor substrates are stacked as shown in FIG. 4 (Step S14). FIG. 8 is a schematic cross-sectional view showing a stacking step following FIG. 7 in the method for manufacturing a semiconductor device according to the present embodiment. When stacking semiconductor substrates, for example, as shown in FIG. 8, a plurality of semiconductor substrates 2 are stacked so that the application surfaces of semiconductor impurity liquid sources of the same conductivity type face each other. In FIG. 8, reference numeral 11-N denotes an N-type impurity.
ここで、もし、隣り合う無機粉末１４同士の間隔が調整されていない場合、無機粉末１４の分布が偏ることで、局所的に半導体基板２間に無機粉末１４が存在しない箇所が生じ得る。この場合、無機粉末１４が局所的に存在しない箇所では、積層される半導体基板２の重力によって半導体基板２間の間隔が狭められてしまう。これにより、半導体基板２同士の間隔が面方向において不均一となり、半導体基板２間の不純物の配置状態も面方向において不均一となる。この結果、不純物の拡散の均一性を維持することが困難となる。 これに対して、本実施形態では、増粘剤１３によって面方向ｄにおいて隣り合う無機粉末１４同士の間隔が調整されていることで、無機粉末１４は、複数の半導体基板２同士の間隔の面方向における分布を調整することができる。例えば、無機粉末１４は、半導体基板２同士の間隔の面方向ｄにおける分布を均一になるように調整することができる。 Here, if the interval between the adjacent inorganic powders 14 is not adjusted, the distribution of the inorganic powders 14 may be uneven, and a portion where the inorganic powders 14 do not exist locally between the semiconductor substrates 2 may be generated. In this case, at locations where the inorganic powder 14 does not locally exist, the distance between the semiconductor substrates 2 is reduced by the gravity of the semiconductor substrates 2 to be stacked. As a result, the spacing between the semiconductor substrates 2 becomes non-uniform in the plane direction, and the arrangement of impurities between the semiconductor substrates 2 also becomes non-uniform in the plane direction. As a result, it becomes difficult to maintain the uniformity of impurity diffusion. On the other hand, in the present embodiment, the interval between the inorganic powders 14 adjacent to each other in the surface direction d is adjusted by the thickener 13. The distribution in the direction can be adjusted. For example, the inorganic powder 14 can be adjusted so that the distribution of the intervals between the semiconductor substrates 2 in the plane direction d is uniform.
このように、半導体基板２同士の間隔の面方向における均一性を高めることができるので、半導体基板２間の不純物の配置状態の面方向における均一性を高めることができる。この結果、不純物の拡散の均一性を高めることができる。 In this manner, the uniformity of the spacing between the semiconductor substrates 2 in the plane direction can be improved, and thus the uniformity of the arrangement state of the impurities between the semiconductor substrates 2 in the plane direction can be improved. As a result, the uniformity of impurity diffusion can be improved.
半導体基板を積層させた後、図４に示すように、不要な物質を除去する焼成工程を実施する（ステップＳ１５）。図９は、本実施形態に係る半導体装置の製造方法において、図８に続く焼成工程を示す概略断面図である。図１０は、本実施形態に係る半導体装置の製造方法において、拡散プロセスでの温度遷移を示すグラフである。焼成工程においては、例えば、図９に示すように、積層された半導体基板２を焼成温度で加熱して増粘剤１３を除去する。より詳しくは、図１０に示すように、積層された半導体基板２を、一定の焼成温度Ｔａで一定時間ｔ１加熱して増粘剤１３を除去する。このとき、Ｐ型半導体不純物液体ソース１−Ｐの塗布の際に増粘剤１３によって無機粉末１４間の間隔ｉが調整されているので、半導体基板２の表面上にＰ型不純物１１−Ｐをできるだけ均一に配置することができる。 After stacking the semiconductor substrates, as shown in FIG. 4, a baking process for removing unnecessary substances is performed (Step S15). FIG. 9 is a schematic cross-sectional view showing a firing step following FIG. 8 in the method for manufacturing a semiconductor device according to the present embodiment. FIG. 10 is a graph showing a temperature transition in a diffusion process in the method for manufacturing a semiconductor device according to the present embodiment. In the firing step, for example, as shown in FIG. 9, the stacked semiconductor substrates 2 are heated at a firing temperature to remove the thickener 13. More specifically, as shown in FIG. 10, the laminated semiconductor substrate 2 is heated at a constant baking temperature Ta for a certain time t1 to remove the thickener 13. At this time, since the gap i between the inorganic powders 14 is adjusted by the thickener 13 when the P-type semiconductor impurity liquid source 1-P is applied, the P-type impurity 11-P is formed on the surface of the semiconductor substrate 2. They can be arranged as uniformly as possible.
焼成の後、図４に示すように、不純物をガラス化して拡散供給源を生成するデポジション工程を実施する（ステップＳ１６）。 After the firing, as shown in FIG. 4, a deposition step of vitrifying the impurities to generate a diffusion source is performed (step S16).
図１１は、本実施形態に係る半導体装置の製造方法において、図９に続くデポジション工程を示す概略断面図である。デポジション工程においては、例えば、図１１に示すように、Ｐ型不純物１１−Ｐをデポジション温度（第２の温度）に加熱することで、Ｐ型不純物１１−Ｐをガラス化して拡散供給源にする。より詳しくは、図１０に示すように、Ｐ型不純物１１−Ｐを、焼成温度Ｔａよりも高温の一定のデポジション温度Ｔｂで、焼成時間ｔ１よりも長い時間ｔ２加熱することで、Ｐ型不純物１１−Ｐを拡散供給源にする。このとき、Ｐ型不純物１１−Ｐは、浅い位置までは拡散される。 FIG. 11 is a schematic cross-sectional view showing a deposition step following FIG. 9 in the method for manufacturing a semiconductor device according to the present embodiment. In the deposition step, for example, as shown in FIG. 11, by heating the P-type impurity 11-P to a deposition temperature (second temperature), the P-type impurity 11-P is vitrified to be diffused. To More specifically, as shown in FIG. 10, the P-type impurity 11-P is heated at a constant deposition temperature Tb higher than the firing temperature Ta and for a time t2 longer than the firing time t1, so that the P-type impurity 11-P is heated. 11-P is the diffusion source. At this time, the P-type impurity 11-P is diffused to a shallow position.
ここで、Ｐ型半導体不純物液体ソース１−Ｐの塗布の際に、増粘剤１３によって隣り合う無機粉末１４間の間隔ｉが調整されているので、半導体基板２の表面上にＰ型不純物１１−Ｐをできるだけ均一に配置することができる。これにより、Ｐ型不純物１１−Ｐをできるだけ均一に拡散させることができる。このことは、Ｎ型不純物１１−Ｎについても同様である。 Here, at the time of application of the P-type semiconductor impurity liquid source 1-P, the distance i between the adjacent inorganic powders 14 is adjusted by the thickener 13 so that the P-type impurity 11 −P can be arranged as uniformly as possible. Thereby, the P-type impurity 11-P can be diffused as uniformly as possible. This is the same for the N-type impurity 11-N.
また、このとき、上下の半導体基板２同士がブロック状態となって接合される。 At this time, the upper and lower semiconductor substrates 2 are joined in a block state.
デポジション工程を実施した後、図４に示すように、所望の深さまで不純物を拡散させる拡散工程を実施する（ステップＳ１７）。図１２は、本実施形態に係る半導体装置の製造方法において、図１１に続く拡散工程を示す概略断面図である。拡散工程においては、例えば、図１２に示すように、Ｐ型不純物１１−Ｐを拡散温度に加熱することで、Ｐ型不純物１１−Ｐを所望の深さまで拡散させる。より詳しくは、図１０に示すように、Ｐ型不純物１１−Ｐを、デポジション温度Ｔｂよりも高温の一定の拡散温度Ｔｃで、デポジション時間ｔ２よりも長い時間ｔ３加熱することで、Ｐ型不純物１１−Ｐを所望の深さまで拡散させる。Ｎ型不純物１１−Ｎについても同様に拡散が行われる。 After performing the deposition step, as shown in FIG. 4, a diffusion step of diffusing impurities to a desired depth is performed (step S17). FIG. 12 is a schematic cross-sectional view showing a diffusion step following FIG. 11 in the method for manufacturing a semiconductor device according to the present embodiment. In the diffusion step, for example, as shown in FIG. 12, the P-type impurity 11-P is diffused to a desired depth by heating the P-type impurity 11-P to a diffusion temperature. More specifically, as shown in FIG. 10, the P-type impurity 11-P is heated at a constant diffusion temperature Tc higher than the deposition temperature Tb for a time t3 longer than the deposition time t2, so that the P-type impurity 11-P is heated. The impurity 11-P is diffused to a desired depth. Diffusion is similarly performed for the N-type impurity 11-N.
拡散工程を実施した後、図４に示すように、積層された半導体基板２を剥離液６に浸漬させる（ステップＳ１８）。図１３は、本実施形態に係る半導体装置の製造方法において、図１２に続く浸漬工程を示す概略断面図である。浸漬の際には、図１３に示すように、無機粉末１４によって半導体基板２同士の間隔が維持されているため、剥離液６は、最外周の無機粉末１４の箇所から中心側に向かって容易に浸透することができる。 After performing the diffusion step, as shown in FIG. 4, the laminated semiconductor substrate 2 is immersed in the stripping solution 6 (Step S18). FIG. 13 is a schematic cross-sectional view showing a dipping step following FIG. 12 in the method for manufacturing a semiconductor device according to the present embodiment. At the time of immersion, as shown in FIG. 13, the interval between the semiconductor substrates 2 is maintained by the inorganic powder 14, so that the stripping solution 6 is easily moved from the outermost portion of the inorganic powder 14 toward the center. Can penetrate.
これにより、半導体基板２同士の剥離が促進されて剥離時間を短縮することができる。 Thereby, the separation between the semiconductor substrates 2 is promoted, and the separation time can be shortened.
剥離液への浸漬の後、図４に示すように、半導体基板２を洗浄、乾燥させて積層状態から剥離する（ステップＳ１９）。 After immersion in the stripping solution, as shown in FIG. 4, the semiconductor substrate 2 is washed, dried, and stripped from the stacked state (step S19).
以下、本実施形態によってもたらされる作用について説明する。 Hereinafter, an operation provided by the present embodiment will be described.
上述したように、本実施形態に係る半導体不純物液体ソースは、不純物を含む化合物と、化合物を溶解する有機溶剤と、有機溶剤に溶解し、半導体不純物液体ソースに粘性を付与する増粘剤と、不純物よりも大きい直径を有する無機粉末と、が混合して含有されている。増粘剤は、半導体不純物液体ソースを半導体基板の塗布面に塗布する際に、半導体不純物液体ソースに付与する粘性によって、塗布面に沿った面方向において隣り合う無機粉末同士の間隔を調整して塗布面上への不純物の分布を調整し、半導体不純物液体ソースを乾燥させる第１の温度に加熱されることで、有機溶剤の蒸発にともなって隣り合う無機粉末同士の間に析出して塗布面上への不純物の分布を維持する特性を有する。無機粉末は、複数の半導体基板を積層する際に、増粘剤によって面方向において隣り合う無機粉末同士の間隔が調整されていることで、複数の半導体基板同士の間隔の面方向における分布を調整し、不純物を第１の温度よりも高い温度である不純物の拡散供給源が生成される第２の温度に加熱した後、第２の温度での加熱によって接合された複数の半導体基板を剥離液に晒す際に、複数の半導体基板同士の間隔を維持していることで、複数の半導体基板間に剥離液を浸透させる特性を有する。 As described above, the semiconductor impurity liquid source according to the present embodiment is a compound containing impurities, an organic solvent that dissolves the compound, a thickener that dissolves in the organic solvent and imparts viscosity to the semiconductor impurity liquid source, And an inorganic powder having a diameter larger than that of the impurities. When the thickener is applied to the application surface of the semiconductor substrate, the viscosity of the semiconductor impurity liquid source is adjusted by adjusting the distance between adjacent inorganic powders in the surface direction along the application surface. By adjusting the distribution of impurities on the coating surface and heating the semiconductor impurity liquid source to a first temperature to dry the semiconductor impurity liquid source, the organic solvent is evaporated and deposited between adjacent inorganic powders to form a coating surface. It has the property of maintaining the distribution of impurities upward. When stacking a plurality of semiconductor substrates, the inorganic powder adjusts the distribution of the spacing between the plurality of semiconductor substrates in the plane direction by adjusting the spacing between the inorganic powders adjacent in the plane direction by the thickener. Then, after the impurities are heated to a second temperature at which an impurity diffusion supply source which is a temperature higher than the first temperature is generated, the plurality of semiconductor substrates joined by the heating at the second temperature are stripped. When the semiconductor substrate is exposed, the gap between the plurality of semiconductor substrates is maintained, so that the semiconductor substrate has a characteristic of allowing the peeling liquid to permeate between the plurality of semiconductor substrates.
このように、本発明によれば、半導体不純物液体ソースを塗布する際に、増粘剤の粘性によって塗布面上への不純物の分布を調整し、半導体不純物液体ソースを第１の温度で乾燥させる際に、増粘剤が隣り合う無機粉末同士の間に析出して塗布面上への不純物の分布を維持し、複数の半導体基板を積層する際に、増粘剤の粘性で面方向の間隔が調整されている無機粉末によって、半導体基板同士の間隔の面方向における分布を調整し、複数の半導体基板を剥離液に晒す際に、無機粉末で維持された半導体基板同士の間隔を介して剥離液を浸透させることができる。 As described above, according to the present invention, when applying the semiconductor impurity liquid source, the distribution of the impurity on the application surface is adjusted by the viscosity of the thickener, and the semiconductor impurity liquid source is dried at the first temperature. At the time, the thickener precipitates between the adjacent inorganic powders to maintain the distribution of impurities on the application surface, and when laminating a plurality of semiconductor substrates, the viscosity of the thickener increases the spacing in the surface direction. By adjusting the distribution of the spacing between the semiconductor substrates in the plane direction by adjusting the inorganic powder, when exposing a plurality of semiconductor substrates to the stripping solution, the separation is performed via the spacing between the semiconductor substrates maintained by the inorganic powder. The liquid can penetrate.
これにより、不純物の拡散の均一性を確保しつつ半導体基板の剥離の所要時間を短縮して半導体装置の製造効率を向上させることができる。 This makes it possible to shorten the time required for peeling the semiconductor substrate and improve the manufacturing efficiency of the semiconductor device while ensuring uniformity of impurity diffusion.
また、ドーパントフィルムでは、大量の有機系バインダによるガスが急激に発生して異常燃焼が生じないように、一定温度でドーパントフィルムをプリベークする必要があるところ、半導体不純物液体ソースでは、異常燃焼が生じない有機溶剤を用いているため、焼成の前のプリベークは不要である。これにより、工程数を抑えて製造効率を更に向上させることができる。 Also, in the dopant film, it is necessary to pre-bake the dopant film at a constant temperature so that a large amount of organic binder gas is generated suddenly and abnormal combustion does not occur.In the semiconductor impurity liquid source, abnormal combustion occurs. Since no organic solvent is used, pre-baking before firing is unnecessary. Thereby, the manufacturing efficiency can be further improved by suppressing the number of steps.
（変形例）
上述した以外にも、本発明には、種々の変形例を適用することができる。(Modification)
Various modifications other than those described above can be applied to the present invention.
図１４は、本実施形態の変形例に係る半導体不純物液体ソースの製造方法を示すフローチャートである。例えば、図１４に示すように、半導体不純物液体ソースを製造する際に、混合液を保持する前に撹拌してもよい（ステップＳ４）。混合液を撹拌することで、増粘剤の粘度を更に安定させることができる。増粘剤の粘度を安定させることで、半導体装置の製造の際に、より効果的に不純物の拡散の均一性を確保することができる。 FIG. 14 is a flowchart illustrating a method for manufacturing a semiconductor impurity liquid source according to a modification of the present embodiment. For example, as shown in FIG. 14, when manufacturing the semiconductor impurity liquid source, stirring may be performed before holding the mixed liquid (step S4). By stirring the mixture, the viscosity of the thickener can be further stabilized. By stabilizing the viscosity of the thickener, uniformity of impurity diffusion can be more effectively ensured in the manufacture of a semiconductor device.
また、半導体不純物液体ソース全体に対する無機粉末の質量濃度（ｗｔ％）は、半導体不純物液体ソース全体に対する増粘剤の質量濃度（ｗｔ％）よりも低くてもよい。ここで、無機粉末の質量濃度が増粘剤の質量濃度よりも高いと、増粘剤が粘性を適切に発揮できず半導体不純物液体ソースが伸びにくくなるため、所望の粘度を得ようとして増粘剤の材料の選定等を行ったとしても、増粘剤の粘度を正確に調整することが困難である。これに対して、無機粉末の質量濃度が増粘剤の質量濃度よりも低ければ、増粘剤が粘性を適切に発揮できるので、所望の粘度を得ようとして増粘剤の材料の選定等を行うことで、増粘剤の粘度を正確に調整することができる。 Further, the mass concentration (wt%) of the inorganic powder with respect to the entire semiconductor impurity liquid source may be lower than the mass concentration (wt%) of the thickener with respect to the entire semiconductor impurity liquid source. Here, when the mass concentration of the inorganic powder is higher than the mass concentration of the thickener, the thickener cannot properly exhibit the viscosity and the semiconductor impurity liquid source becomes difficult to expand, so that the viscosity is increased in order to obtain a desired viscosity. Even if the material of the agent is selected, it is difficult to accurately adjust the viscosity of the thickener. On the other hand, if the mass concentration of the inorganic powder is lower than the mass concentration of the thickener, the viscosity of the thickener can be appropriately exerted. By doing so, the viscosity of the thickener can be adjusted accurately.
また、半導体不純物液体ソース全体に対する無機粉末の質量濃度は、半導体不純物液体ソース全体に対する有機溶剤の質量濃度よりも低くてもよい。ここで、無機粉末の質量濃度が有機溶剤の質量濃度よりも高いと、半導体不純物液体ソースの流動性が著しく損なわれた状態になるので、流動体に粘性を付与する増粘剤が加わっても、粘性を付与すべき流動体（有機溶剤）が少な過ぎるので、増粘剤が適切に粘性を発揮できない。このため、所望の粘度を得ようとして増粘剤の材料の選定等を行ったとしても、増粘剤の粘度を正確に調整することは困難である。これに対して、無機粉末の質量濃度が有機溶剤の質量濃度よりも低ければ、粘性を付与する十分な有機溶剤を確保することができるので、増粘剤が粘性を適切に発揮できる。このため、所望の粘度を得ようとして増粘剤の材料の選定等を行うことで、増粘剤の粘度を正確に調整することができる。 Further, the mass concentration of the inorganic powder with respect to the entire semiconductor impurity liquid source may be lower than the mass concentration of the organic solvent with respect to the entire semiconductor impurity liquid source. Here, if the mass concentration of the inorganic powder is higher than the mass concentration of the organic solvent, the fluidity of the semiconductor impurity liquid source becomes significantly impaired, so even if a thickener that imparts viscosity to the fluid is added. Since the fluid (organic solvent) to be provided with the viscosity is too small, the thickener cannot properly exhibit the viscosity. For this reason, it is difficult to accurately adjust the viscosity of the thickener even if the material of the thickener is selected in order to obtain a desired viscosity. On the other hand, if the mass concentration of the inorganic powder is lower than the mass concentration of the organic solvent, a sufficient organic solvent for imparting viscosity can be secured, so that the thickener can properly exhibit the viscosity. Therefore, the viscosity of the thickener can be accurately adjusted by selecting the material of the thickener in order to obtain a desired viscosity.
上記の記載に基づいて、当業者であれば、本発明の追加の効果や種々の変形を想到できるかもしれないが、本発明の態様は、上述した個々の実施形態に限定されるものではない。異なる実施形態にわたる構成要素を適宜組み合わせてもよい。特許請求の範囲に規定された内容及びその均等物から導き出される本発明の概念的な思想と趣旨を逸脱しない範囲で種々の追加、変更及び部分的削除が可能である。 Based on the above description, those skilled in the art may be able to conceive additional effects and various modifications of the present invention, but aspects of the present invention are not limited to the above-described individual embodiments. . Components of different embodiments may be appropriately combined. Various additions, changes, and partial deletions can be made without departing from the concept and spirit of the present invention derived from the contents defined in the claims and equivalents thereof.
１−Ｐ Ｐ型半導体不純物液体ソース
１−Ｎ Ｎ型半導体不純物液体ソース
１１−Ｐ Ｐ型不純物
１１−Ｎ Ｎ型不純物
１２ 有機溶剤
１３ 増粘剤
１４ 無機粉末1-PP P-type semiconductor impurity liquid source 1-N N-type semiconductor impurity liquid source 11-PP P-type impurity 11-N N-type impurity 12 Organic solvent 13 Thickener 14 Inorganic powder
Claims (14)
前記不純物を含む化合物と、
前記化合物を溶解する有機溶剤と、
前記有機溶剤に溶解し、前記半導体不純物液体ソースに粘性を付与する増粘剤と、
前記不純物よりも大きい直径を有する無機粉末と、が混合して含有され、
前記増粘剤は、
前記半導体不純物液体ソースを前記半導体基板の塗布面に塗布する際に、前記半導体不純物液体ソースに付与する前記粘性によって、前記塗布面に沿った面方向において隣り合う前記無機粉末同士の間隔を調整して前記塗布面上への前記不純物の分布を調整し、
前記半導体不純物液体ソースを乾燥させる第１の温度に加熱されることで、前記有機溶剤の蒸発にともなって前記隣り合う無機粉末同士の間に析出して前記塗布面上への前記不純物の分布を維持する特性を有し、
前記無機粉末は、
前記複数の半導体基板を積層させる際に、前記増粘剤によって前記面方向において隣り合う無機粉末同士の間隔が調整されていることで、前記複数の半導体基板同士の間隔の前記面方向における分布を調整し、
前記不純物を前記第１の温度よりも高い温度である前記不純物の拡散供給源が生成される第２の温度に加熱した後、前記第２の温度での加熱によって接合された前記複数の半導体基板を剥離液に晒す際に、前記複数の半導体基板同士の間隔を維持していることで、前記複数の半導体基板間に前記剥離液を浸透させる特性を有することを特徴とする半導体不純物液体ソース。A semiconductor impurity liquid source that diffuses impurities into the plurality of semiconductor substrates by being heated while being applied between the plurality of stacked semiconductor substrates,
A compound containing the impurity,
An organic solvent that dissolves the compound,
A thickener that is dissolved in the organic solvent and imparts viscosity to the semiconductor impurity liquid source,
And an inorganic powder having a diameter larger than the impurities,
The thickener is
When applying the semiconductor impurity liquid source to the application surface of the semiconductor substrate, the viscosity provided to the semiconductor impurity liquid source adjusts a distance between the inorganic powders adjacent in a surface direction along the application surface. Adjusting the distribution of the impurities on the coating surface,
By being heated to a first temperature for drying the semiconductor impurity liquid source, with the evaporation of the organic solvent, it is deposited between the adjacent inorganic powders and the distribution of the impurity on the application surface is reduced. Has the property of maintaining,
The inorganic powder,
When laminating the plurality of semiconductor substrates, by adjusting the interval between the inorganic powder adjacent in the surface direction by the thickener, the distribution of the interval between the plurality of semiconductor substrates in the surface direction. Adjust,
The plurality of semiconductor substrates joined by heating the impurity to a second temperature, which is higher than the first temperature, at which the impurity diffusion supply source is generated, and then heating the impurity at the second temperature A semiconductor impurity liquid source having a property of allowing the stripping solution to permeate between the plurality of semiconductor substrates by maintaining a distance between the plurality of semiconductor substrates when exposing the semiconductor substrate to the stripping solution.
前記不純物を含む化合物と、前記化合物を溶解する有機溶剤と、前記有機溶剤に溶解し、前記半導体不純物液体ソースに粘性を付与する増粘剤と、を混合した混合液を生成する工程と、
前記混合液の粘性を安定させるために前記混合液を予め決められた時間所定の雰囲気下で保持する工程と、
前記保持の後に、前記混合液に、前記不純物よりも大きい直径を有する無機粉末を混合する工程と、を備えることを特徴とする半導体不純物液体ソースの製造方法。A method for manufacturing a semiconductor impurity liquid source according to claim 1, wherein
A step of producing a mixed solution of a compound containing the impurity, an organic solvent for dissolving the compound, and a thickener that dissolves in the organic solvent and imparts viscosity to the semiconductor impurity liquid source,
A step of maintaining the mixture under a predetermined atmosphere for a predetermined time to stabilize the viscosity of the mixture,
Mixing the mixed liquid with an inorganic powder having a diameter larger than that of the impurities after the holding.
前記塗布された半導体不純物液体ソースを第１の温度に加熱することで、前記塗布された半導体不純物液体ソースを乾燥させる工程と、
前記複数の半導体基板を積層させる工程と、
前記前記複数の半導体基板を積層させる際に、前記無機粉末によって前記複数の半導体基板同士の間隔の分布を調整する工程と、
前記不純物を第２の温度に加熱することで、前記不純物の拡散供給源を生成する工程と、
前記複数の半導体基板を剥離液に浸漬させて、前記第２の温度での加熱によって接合された前記複数の半導体基板同士を剥離する工程と、を備えることを特徴とする半導体装置の製造方法。Applying a semiconductor impurity liquid source according to claim 1 to a plurality of semiconductor substrates;
Drying the applied semiconductor impurity liquid source by heating the applied semiconductor impurity liquid source to a first temperature;
Laminating the plurality of semiconductor substrates,
Adjusting the distribution of the intervals between the plurality of semiconductor substrates by the inorganic powder when stacking the plurality of semiconductor substrates;
Generating a diffusion source of the impurity by heating the impurity to a second temperature;
And dipping the plurality of semiconductor substrates in a stripping liquid to separate the plurality of semiconductor substrates joined by heating at the second temperature.
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