JP2008159748A - Method for manufacturing solid-state image sensing device and solid-state image sensing device - Google Patents

Method for manufacturing solid-state image sensing device and solid-state image sensing device Download PDF

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JP2008159748A
JP2008159748A JP2006345580A JP2006345580A JP2008159748A JP 2008159748 A JP2008159748 A JP 2008159748A JP 2006345580 A JP2006345580 A JP 2006345580A JP 2006345580 A JP2006345580 A JP 2006345580A JP 2008159748 A JP2008159748 A JP 2008159748A
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film layer
solid
transparent resin
silicon nitride
layer
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Mitsuhiro Nakao
充宏 中尾
Tadashi Ishimatsu
忠 石松
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Toppan Inc
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Toppan Printing Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a solid-state image sensing device by which space between inorganic micro-lenses is set to 0.1 μm or less and an aperture ratio is improved and to provide a high-sensitivity solid-state image sensing device. <P>SOLUTION: The method for manufacturing the solid-state image sensing device is provided with a process for forming a silicon oxide film layer or a silicon nitride film layer by CVD above a photoelectric conversion part, a process for stacking a transparent resin layer on the above layer, a process for forming a lens mother die by using a photosensitive resin exhibiting thermal reflow properties and alkali solubility on the transparent resin layer and a process for dry etching the lens mother die and, transferring the pattern of the lens mother die to the silicon oxide film layer or the silicon nitride film layer through the transparent resin layer to form micro-lenses. In this case, the transparent resin is acrylic resin or phenol resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、ＣＭＯＳやＣＣＤなどの固体撮像素子に関するものであり、特に、レンズ間スペースが０．１μｍ以下と狭く、マイクロレンズの開口率の高い固体撮像素子の製造方法、及び固体撮像素子に関する。   The present invention relates to a solid-state imaging device such as a CMOS or a CCD, and more particularly to a method for manufacturing a solid-state imaging device having a small space between lenses of 0.1 μm or less and a high aperture ratio of a microlens, and a solid-state imaging device.

ＣＭＯＳやＣＣＤなどの固体撮像素子には、入射した光を光電変換部へ集光させるために、複数の光電変換部の各々に対応したマイクロレンズが設けられている。図１（ａ）〜（ｃ）は、マイクロレンズを形成する方法の一例を断面で示す説明図である。   A solid-state imaging device such as a CMOS or a CCD is provided with a microlens corresponding to each of the plurality of photoelectric conversion units in order to collect incident light onto the photoelectric conversion unit. FIGS. 1A to 1C are explanatory views showing in cross section an example of a method for forming a microlens.

図１（ａ）に示すように、光電変換部（１０）が形成された半導体基板（１１）上にシリコン窒化膜層（１２）を形成後、図１（ｂ）に示すように、熱リフロー性をもつ感光性樹脂をレンズ母型形成用のレンズ材料として塗布し、露光、現像、熱リフローさせて凸レンズ形状を有するレンズ母型（１５）とする。
次に、図１（ｃ）に示すように、ドライエッチング装置にて、レンズ母型（１５）を形成した半導体基板（１１）にドライエッチング処理（白矢印）を行って、下方のシリコン窒化膜層（１２）にレンズ母型（１５）のパターン形状を転写し、マイクロレンズ（１６）とする。 As shown in FIG. 1A, after forming a silicon nitride film layer 12 on the semiconductor substrate 11 on which the photoelectric conversion portion 10 is formed, thermal reflow is performed as shown in FIG. A photosensitive resin having a property is applied as a lens material for forming a lens matrix, and is exposed, developed, and thermally reflowed to obtain a lens matrix (15) having a convex lens shape.
Next, as shown in FIG. 1C, dry etching (white arrow) is performed on the semiconductor substrate (11) on which the lens matrix (15) is formed by a dry etching apparatus, and the silicon nitride film below The pattern shape of the lens matrix (15) is transferred to the layer (12) to form a microlens (16).

このシリコン窒化膜を用いたマイクロレンズ（１６）は、レンズ間スペース（Ｗ１）が０．３μｍ程度を有し、マイクロレンズの開口率は小さい。つまり、このようなマイクロレンズを有する固体撮像素子の感度は低いものとなる。
特開２００６−１１４５９４号公報 特開平１０−１４８７０４号公報 The microlens (16) using this silicon nitride film has an inter-lens space (W1) of about 0.3 μm, and the aperture ratio of the microlens is small. That is, the sensitivity of the solid-state imaging device having such a microlens is low.
JP 2006-114594 A Japanese Patent Laid-Open No. 10-148704

本発明は、上記の問題に鑑みてなされたものであり、シリコン窒化膜のような無機マイクロレンズにて、レンズ間スペースを０．１μｍ以下の狭いものとし、マイクロレンズの開口率を向上させることのできる固体撮像素子の製造方法を提供することを課題とするものである。また、上記固体撮像素子の製造方法を用いて製造した高感度の固体撮像素子を提供することを課題とする。   The present invention has been made in view of the above problems, and in an inorganic microlens such as a silicon nitride film, the space between lenses is narrowed to 0.1 μm or less, and the aperture ratio of the microlens is improved. It is an object of the present invention to provide a method for manufacturing a solid-state imaging device that can be used. It is another object of the present invention to provide a high-sensitivity solid-state image sensor manufactured using the above-described method for manufacturing a solid-state image sensor.

本発明は、複数の光電変換部上方に、その各々に対応したマイクロレンズが設けられた固体撮像素子の製造方法において、
１）半導体基板の前記光電変換部上方に、ＣＶＤ（化学気相成長法）によりシリコン酸化膜層もしくはシリコン窒化膜層を形成する工程、
２）該シリコン酸化膜層もしくはシリコン窒化膜層上に透明樹脂層を積層する工程、
３）該透明樹脂層上に、熱リフロー性を有するアルカリ可溶性の感光性樹脂をレンズ母型形成用のレンズ材料として用い、フォトリソグラフィ及び熱リフロー処理によってレンズ母型を形成する工程、
４）該レンズ母型にドライエッチングを行い、レンズ母型のパターンを透明樹脂層を介しシリコン酸化膜層もしくはシリコン窒化膜層に転写し、シリコン酸化膜層もしくはシリコン窒化膜層をマイクロレンズとする工程、
を少なくとも具備することを特徴とする固体撮像素子の製造方法である。 The present invention provides a solid-state imaging device manufacturing method in which a microlens corresponding to each of the plurality of photoelectric conversion units is provided above,
1) forming a silicon oxide film layer or a silicon nitride film layer by CVD (chemical vapor deposition) above the photoelectric conversion portion of a semiconductor substrate;
2) a step of laminating a transparent resin layer on the silicon oxide film layer or silicon nitride film layer;
3) A step of forming a lens matrix by photolithography and thermal reflow treatment on the transparent resin layer using an alkali-soluble photosensitive resin having thermal reflow properties as a lens material for forming the lens matrix;
4) The lens matrix is dry-etched, the lens matrix pattern is transferred to the silicon oxide film layer or silicon nitride film layer through the transparent resin layer, and the silicon oxide film layer or silicon nitride film layer is used as a microlens. Process,
A solid-state imaging device manufacturing method characterized by comprising:

また、本発明は、上記発明による固体撮像素子の製造方法において、前記透明樹脂層の形成に用いる透明樹脂が、アクリル樹脂もしくはフェノール樹脂であることを特徴とする固体撮像素子の製造方法である。   According to another aspect of the present invention, there is provided a method for manufacturing a solid-state imaging device, wherein the transparent resin used for forming the transparent resin layer is an acrylic resin or a phenol resin.

また、本発明は、請求項１又は請求項２記載の固体撮像素子の製造方法を用いて製造した固体撮像素子であって、マイクロレンズのレンズ間スペースが０．１μｍ以下であることを特徴とする固体撮像素子である。   Further, the present invention is a solid-state imaging device manufactured by using the method for manufacturing a solid-state imaging device according to claim 1 or 2, wherein a space between microlenses is 0.1 μm or less. A solid-state imaging device.

本発明は、半導体基板の光電変換部上方に、ＣＶＤによりシリコン酸化膜層もしくはシリコン窒化膜層を形成する工程、シリコン酸化膜層もしくはシリコン窒化膜層上に透明樹脂層を積層する工程、透明樹脂層上に熱リフロー性を有するアルカリ可溶性の感光性樹脂をレンズ母型形成用のレンズ材料として用い、フォトリソグラフィ及び熱リフロー処理によってレンズ母型を形成する工程、レンズ母型にドライエッチングを行い、レンズ母型のパターンを透明樹脂層を介しシリコン酸化膜層もしくはシリコン窒化膜層に転写し、シリコン酸化膜層もしくはシリコン窒化膜層をマイクロレンズとする工程を少なくとも具備する固体撮像素子の製造方法であるので、無機のマイクロレンズにて、レンズ間スペースを０．１μｍ以下の狭いものとし、マイクロレンズの開口率を向上させることのできる固体撮像素子の製造方法となる。   The present invention includes a step of forming a silicon oxide film layer or a silicon nitride film layer by CVD above a photoelectric conversion portion of a semiconductor substrate, a step of laminating a transparent resin layer on the silicon oxide film layer or the silicon nitride film layer, a transparent resin Using an alkali-soluble photosensitive resin having thermal reflow on the layer as a lens material for forming a lens matrix, a process for forming a lens matrix by photolithography and thermal reflow treatment, dry etching is performed on the lens matrix, A method of manufacturing a solid-state imaging device, comprising at least a step of transferring a lens matrix pattern to a silicon oxide film layer or silicon nitride film layer through a transparent resin layer, and using the silicon oxide film layer or silicon nitride film layer as a microlens. Because there is an inorganic microlens, the space between the lenses should be 0.1 μm or less. A manufacturing method of a solid-state imaging device capable of improving the aperture ratio of the microlens.

また、本発明は、上記固体撮像素子の製造方法を用いて製造した固体撮像素子であるので、マイクロレンズのレンズ間スペースが０．１μｍ以下となり高感度の固体撮像素子を提供することができる。   In addition, since the present invention is a solid-state image sensor manufactured using the above-described method for manufacturing a solid-state image sensor, the space between the lenses of the microlens is 0.1 μm or less, and a highly sensitive solid-state image sensor can be provided.

以下に本発明による固体撮像素子の製造方法、及び固体撮像素子を実施形態に基づいて説明する。
図２（ａ）〜（ｅ）は、本発明による固体撮像素子の製造方法の一実施例を断面で示す説明図である。図２（ａ）に示すように、先ず、半導体基板（１１）の光電変換部（１０）上方に、ＣＶＤ（化学気相成長法）によりシリコン酸化膜層もしくはシリコン窒化膜層（２２）を形成する。次に、図２（ｂ）に示すように、シリコン酸化膜層もしくはシリコン窒化膜層（２２）上に透明樹脂層（１３）を積層する。 A solid-state image sensor manufacturing method and a solid-state image sensor according to the present invention will be described below based on embodiments.
FIGS. 2A to 2E are explanatory views showing in cross section one embodiment of a method for manufacturing a solid-state imaging device according to the present invention. As shown in FIG. 2A, first, a silicon oxide film layer or a silicon nitride film layer (22) is formed above the photoelectric conversion portion (10) of the semiconductor substrate (11) by CVD (chemical vapor deposition). To do. Next, as shown in FIG. 2B, a transparent resin layer (13) is laminated on the silicon oxide film layer or the silicon nitride film layer (22).

次に、図２（ｃ）に示すように、透明樹脂層（１３）上に、熱リフロー性を有するアルカリ可溶性の感光性樹脂をレンズ母型形成用のレンズ材料として用い、フォトリソグラフィ及び熱リフロー処理によってレンズ母型（１５）を形成する。次に、図２（ｄ）〜（ｅ）に示すように、レンズ母型（１５）にドライエッチング（白矢印）を行い、レンズ母型（１５）のパターンを透明樹脂層（１３）を介しシリコン酸化膜層もしくはシリコン窒化膜層（２２）に転写し、シリコン酸化膜層もしくはシリコン窒化膜層をマイクロレンズ（２６）とする。   Next, as shown in FIG. 2C, an alkali-soluble photosensitive resin having thermal reflow properties is used as a lens material for forming a lens matrix on the transparent resin layer (13), and photolithography and thermal reflow are performed. A lens matrix (15) is formed by processing. Next, as shown in FIGS. 2D to 2E, the lens matrix (15) is dry-etched (white arrow), and the pattern of the lens matrix (15) is passed through the transparent resin layer (13). It transfers to a silicon oxide film layer or a silicon nitride film layer (22), and let a silicon oxide film layer or a silicon nitride film layer be a micro lens (26).

上記、レンズ母型（１５）にドライエッチング（白矢印）を行い、レンズ母型（１５）のパターンを透明樹脂層（１３）を介しシリコン酸化膜層もしくはシリコン窒化膜層（２２）に転写し、マイクロレンズ（２６）を形成する工程は、図２（ｃ）に示す状態から、図２（ｅ）に示す状態へと連続して行われるのであるが、その途上における透明樹脂層（１３）のマイクロレンズ（２３）が形成される状態を、図２（ｄ）に模式的に表している。   The lens matrix (15) is dry etched (white arrow), and the pattern of the lens matrix (15) is transferred to the silicon oxide film layer or silicon nitride film layer (22) through the transparent resin layer (13). The step of forming the microlens (26) is continuously performed from the state shown in FIG. 2 (c) to the state shown in FIG. 2 (e), and the transparent resin layer (13) in the process is formed. A state in which the microlens (23) is formed is schematically shown in FIG.

その途上において、ドライエッチングによりレンズ母型（１５）のパターンを透明樹脂層（１３）に転写することで、レンズ間スペース（Ｗ３）を実質的に約０μｍとした透明樹脂層（１３）からなるマイクロレンズ（２３）を形成する。その後に続くドライエッチングにより、このマイクロレンズ（２３）のパターンをシリコン酸化膜層もしくはシリコン窒化膜層（２２）に転写することによって、レンズ間スペース（Ｗ４）が０．１μｍ以下のシリコン酸化膜層もしくはシリコン窒化膜層からなるマイクロレンズ（２６）を形成することができる。   In the process, the pattern of the lens matrix (15) is transferred to the transparent resin layer (13) by dry etching, so that the space between the lenses (W3) is substantially 0 μm. A microlens (23) is formed. By transferring the pattern of the microlens (23) to the silicon oxide film layer or the silicon nitride film layer (22) by subsequent dry etching, a silicon oxide film layer having a lens-to-lens space (W4) of 0.1 μm or less. Alternatively, a microlens (26) made of a silicon nitride film layer can be formed.

本発明における透明樹脂層（１３）の形成に用いる透明樹脂としては、アクリル樹脂もしくはフェノール樹脂であることが好ましい。アクリル樹脂もしくはフェノール樹脂を用いることにより、上記レンズ間スペース（Ｗ３）が約０μｍのマイクロレンズ（２３）の形成が容易になり、レンズ間スペース（Ｗ４）が０．１μｍ以下の無機のマイクロレンズ（２６）を形成することが可能となる。
また、アクリル樹脂もしくはフェノール樹脂を用いることにより、マイクロレンズ表面荒れを微小なものとすることができる。 The transparent resin used for forming the transparent resin layer (13) in the present invention is preferably an acrylic resin or a phenol resin. By using an acrylic resin or a phenol resin, it becomes easy to form the microlens (23) having the inter-lens space (W3) of about 0 μm, and the inorganic microlens having the inter-lens space (W4) of 0.1 μm or less ( 26) can be formed.
Further, by using an acrylic resin or a phenol resin, the surface roughness of the microlens can be made minute.

以下に、実施例により本発明による固体撮像素子の製造方法を具体的に説明する。
図２（ａ）に示すように、先ず、光電変換部（１０）を形成した半導体基板（１１）上に、ＣＶＤによりシリコン窒化膜層（１２）を膜厚（Ｔ１）１．０μｍに形成した。次に、図２（ｂ）に示すように、シリコン窒化膜層（１２）上に透明フェノール樹脂塗布液を用いて、スピンコートにて透明樹脂層（１３）を１．４μｍの膜厚（Ｔ２）で塗布し、２００℃で６分間の加熱により硬膜化処理を行った。 Hereinafter, a method for manufacturing a solid-state imaging device according to the present invention will be described in detail by way of examples.
As shown in FIG. 2A, first, a silicon nitride film layer (12) having a film thickness (T1) of 1.0 μm was formed by CVD on a semiconductor substrate (11) on which a photoelectric conversion portion (10) was formed. . Next, as shown in FIG. 2B, a transparent phenol resin coating solution is used on the silicon nitride film layer (12), and the transparent resin layer (13) is spin-coated to a thickness of 1.4 μm (T2 The film was hardened by heating at 200 ° C. for 6 minutes.

次に、図２（ｃ）に示すように、レンズ母型形成用のレンズ材料として、熱リフロー性を有するアルカリ可溶性の感光性樹脂を公知のフォトリソグラフィ法にて断面形状が矩形のパターンとし、２００℃の熱リフローにより半球状のレンズ母型（１５）を形成した。図３（ａ）、（ｂ）にＳＥＭ写真で示すように、片側０．１５μｍの熱リフロー量（図示せず）で、高さ（Ｈ１）０．５４μｍ、レンズ間スペース（Ｗ２）が０．２５μｍのレンズ母型（１５）が得られた。   Next, as shown in FIG. 2C, as a lens material for forming a lens matrix, an alkali-soluble photosensitive resin having thermal reflow properties is formed into a pattern having a rectangular cross-section by a known photolithography method. A hemispherical lens matrix (15) was formed by thermal reflow at 200 ° C. As shown in SEM photographs in FIGS. 3A and 3B, the thermal reflow amount (not shown) on one side is 0.15 μm, the height (H1) is 0.54 μm, and the inter-lens space (W2) is 0. A lens matrix (15) of 25 μm was obtained.

次に、図２（ｄ）、（ｅ）に示すように、ドライエッチング装置にて、フロン系ガスＣＦ4 とＣ4 Ｆ8 の混合ガスを用い、レンズ母型（１５）をマスクとし、ドライエッチング処理し、転写による無機のマイクロレンズ（２６）を形成した。図４（ａ）、（ｂ）にＳＥＭ写真で示すように、マイクロレンズ（２６）のレンズ間スペース（Ｗ４）は０．０９μｍと狭く加工することができた。また、マイクロレンズ（２６）の高さ（Ｈ２）は０．８６μｍであり、シリコン窒化膜層（１２）はマイクロレンズ下に厚さ（Ｄ）０．０５μｍを残した。
尚、実施例におけるシリコン窒化膜のエッチングレートは、透明樹脂のエッチングレートと比較して１．６倍速いものであった。 Next, as shown in FIGS. 2D and 2E, a dry etching apparatus uses a mixed gas of chlorofluorocarbon gas CF 4 and C 4 F 8 , and the lens matrix (15) is used as a mask to dry. Etching was performed to form an inorganic microlens (26) by transfer. As shown by SEM photographs in FIGS. 4A and 4B, the space (W4) between the lenses of the microlens (26) was as narrow as 0.09 μm. The height (H2) of the microlens (26) was 0.86 μm, and the silicon nitride film layer (12) remained 0.05 μm in thickness (D) under the microlens.
In the examples, the etching rate of the silicon nitride film was 1.6 times faster than the etching rate of the transparent resin.

（ａ）〜（ｃ）は、マイクロレンズを形成する方法の一例を断面で示す説明図である。(A)-(c) is explanatory drawing which shows an example of the method of forming a micro lens in a cross section. （ａ）〜（ｅ）は、本発明による固体撮像素子の製造方法の一実施例を断面で示す説明図である。(A)-(e) is explanatory drawing which shows in cross section one Example of the manufacturing method of the solid-state image sensor by this invention. （ａ）は、実施例におけるレンズ母型表面の状態を示すＳＥＭ写真である。（ｂ）は、実施例におけるレンズ母型の断面を示すＳＥＭ写真である。(A) is a SEM photograph which shows the state of the lens mother die surface in an Example. (B) is the SEM photograph which shows the cross section of the lens mother die in an Example. （ａ）は、実施例におけるマイクロレンズ表面の状態を示すＳＥＭ写真である。（ｂ）は、実施例におけるマイクロレンズの断面を示すＳＥＭ写真である。(A) is a SEM photograph which shows the state of the micro lens surface in an Example. (B) is the SEM photograph which shows the cross section of the micro lens in an Example.

符号の説明Explanation of symbols

１０・・・光電変換部
１１・・・半導体基板
１２・・・シリコン窒化膜層
１３・・・透明樹脂層
１５・・・レンズ母型
１６・・・シリコン窒化膜のマイクロレンズ
２２・・・シリコン酸化膜層もしくはシリコン窒化膜層
２３・・・ドライエッチング途上における透明樹脂層のマイクロレンズ
２６・・・本発明におけるマイクロレンズ
Ｄ・・・マイクロレンズ下に残るシリコン窒化膜層の厚さ
Ｈ１・・・レンズ母型の高さ
Ｈ２・・・マイクロレンズの高さ
Ｔ１・・・シリコン窒化膜層の膜厚
Ｔ２・・・透明樹脂層の膜厚
Ｗ１・・・従来の技術によるマイクロレンズのレンズ間スペース
Ｗ２・・・レンズ母型のレンズ間スペース
Ｗ３・・・透明樹脂層のマイクロレンズのレンズ間スペース
Ｗ４・・・本発明におけるマイクロレンズのレンズ間スペース DESCRIPTION OF SYMBOLS 10 ... Photoelectric conversion part 11 ... Semiconductor substrate 12 ... Silicon nitride film layer 13 ... Transparent resin layer 15 ... Lens matrix 16 ... Micro lens 22 of silicon nitride film ... Silicon Oxide film layer or silicon nitride film layer 23... Micro lens 26 of transparent resin layer in the course of dry etching... Micro lens D in the present invention... Thickness H 1 of silicon nitride film layer remaining under micro lens · Lens matrix height H2 · Microlens height T1 · Silicon nitride film layer thickness T2 · Transparent resin layer thickness W1 · · · · between the lenses of the conventional microlens Space W2 ··· Lens space W3 · · · Lens space W3 · · · Inter-lens space W4 · · · of the microlens in the present invention Scan

Claims (3)

複数の光電変換部上方に、その各々に対応したマイクロレンズが設けられた固体撮像素子の製造方法において、
１）半導体基板の前記光電変換部上方に、ＣＶＤ（化学気相成長法）によりシリコン酸化膜層もしくはシリコン窒化膜層を形成する工程、
２）該シリコン酸化膜層もしくはシリコン窒化膜層上に透明樹脂層を積層する工程、
３）該透明樹脂層上に、熱リフロー性を有するアルカリ可溶性の感光性樹脂をレンズ母型形成用のレンズ材料として用い、フォトリソグラフィ及び熱リフロー処理によってレンズ母型を形成する工程、
４）該レンズ母型にドライエッチングを行い、レンズ母型のパターンを透明樹脂層を介しシリコン酸化膜層もしくはシリコン窒化膜層に転写し、シリコン酸化膜層もしくはシリコン窒化膜層をマイクロレンズとする工程、
を少なくとも具備することを特徴とする固体撮像素子の製造方法。 In the manufacturing method of the solid-state imaging device in which the microlens corresponding to each of the plurality of photoelectric conversion units is provided,
1) forming a silicon oxide film layer or a silicon nitride film layer by CVD (chemical vapor deposition) above the photoelectric conversion portion of a semiconductor substrate;
2) a step of laminating a transparent resin layer on the silicon oxide film layer or silicon nitride film layer;
3) A step of forming a lens matrix by photolithography and thermal reflow treatment on the transparent resin layer using an alkali-soluble photosensitive resin having thermal reflow properties as a lens material for forming the lens matrix;
4) The lens matrix is dry-etched, the lens matrix pattern is transferred to the silicon oxide film layer or silicon nitride film layer through the transparent resin layer, and the silicon oxide film layer or silicon nitride film layer is used as a microlens. Process,
A method for manufacturing a solid-state imaging device, comprising: 前記透明樹脂層の形成に用いる透明樹脂が、アクリル樹脂もしくはフェノール樹脂であることを特徴とする請求項１記載の固体撮像素子の製造方法。   The method for producing a solid-state imaging device according to claim 1, wherein the transparent resin used for forming the transparent resin layer is an acrylic resin or a phenol resin. 請求項１又は請求項２記載の固体撮像素子の製造方法を用いて製造した固体撮像素子であって、マイクロレンズのレンズ間スペースが０．１μｍ以下であることを特徴とする固体撮像素子。   A solid-state imaging device manufactured using the method for manufacturing a solid-state imaging device according to claim 1, wherein a space between lenses of the microlens is 0.1 μm or less.
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