JP2022030453A - 固体撮像素子の製造方法、積層体、及びドライフィルム - Google Patents
固体撮像素子の製造方法、積層体、及びドライフィルム Download PDFInfo
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Images
Classifications
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- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
Description
光電変換層を備える、第1積層体を準備する、第1積層体準備工程と、
支持層と、支持層の一方の面に積層された接着層とを備える、第2積層体を準備する、第2積層体準備工程と、
第1積層体と、第2積層体とを貼り合わせて第3積層体を得る、貼り合わせ工程と、
貼り合わせ工程後に、接着層を露光及び/又は加熱により硬化させて接着層を近赤外線吸収層とする、硬化工程と、を含み、
第1積層体が、光電変換層と、光電変換層上のカラーフィルター層と、カラーフィルター層上のレンズと、レンズを被覆する平坦化層とを備え、
接着層が、硬化性化合物と、近赤外吸収化合物とを含み、
硬化性化合物が、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物であり、
第3積層体において、平坦化層の表面と、接着層の表面とが貼り合わせられている、固体撮像素子の製造方法である。
支持層と、支持層の一方の面に積層された接着層とを備え、
接着層が、硬化性化合物と、近赤外吸収化合物とを含み、
硬化性化合物が、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物である、
固体撮像素子において近赤外線吸収層を形成するために用いられる積層体である。
基材フィルムと、基材フィルムの表面に形成された接着層とを備え、
接着層が、硬化性化合物と、近赤外吸収化合物とを含み、
硬化性化合物が、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物であり、
基材フィルムが、接着層から剥離可能である、
固体撮像素子において近赤外線吸収層を形成するために用いられる、ドライフィルムである。
固体撮像素子の製造方法は、
光電変換層を備える、第1積層体を準備する、第1積層体準備工程と、
支持層と、支持層の一方の面に積層された接着層とを備える、第2積層体を準備する、第2積層体準備工程と、
第1積層体と、第2積層体とを貼り合わせて第3積層体を得る、貼り合わせ工程と、
貼り合わせ工程後に、接着層を露光及び/又は加熱により硬化させて接着層を近赤外線吸収層とする、硬化工程と、を含む。
第1積層体は、光電変換層と、光電変換層上のカラーフィルター層と、カラーフィルター層上のレンズと、レンズを被覆する平坦化層とを備える。
接着層は、硬化性化合物と、近赤外吸収化合物とを含む。
硬化性化合物は、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物である。
第3積層体において、平坦化層の表面と、接着層の表面とが貼り合わせられている。
第1積層体準備工程では、光電変換層11を備える、第1積層体10Aを準備する。
図1に示されるように、第1積層体11は、光電変換層11と、光電変換層11上のカラーフィルター層12と、カラーフィルター層12上のレンズ13と、レンズ13を被覆する平坦化層14とを備える。
光電変換層11、カラーフィルター層12、レンズ13、及び平坦化層14は、それぞれ公知の方法により形成され得る。
光電変換層11の構造は、特に限定されない。光電変換層11の構造としては、CCD構造やCMOS構造等を採用できる。光電変換部11Bは、例えば基板11Aにおいて、線状、又は行列状に配置され得る。
上記の無機材料以外に、エピスルフィド系樹脂、チエタン化合物、及びチエタン化合物の樹脂等の高屈折率を示す有機材料を用いることができる。金属チエタン化合物や、金属チエタン化合物を含む重合性組成物を用いることにより、特に屈折率の高いレンズ13を形成できる。
さらに、これらの樹脂に、TiO2、ZrO2、Ta2O5、Nb2O5、ZnO、及びSi3N4等の2~2.5程度の高屈折率を示す酸化物や窒化物を添加することにより、より高屈折率が高いレンズ13を形成できる。
第2積層体準備工程では、支持層16と、支持層の一方の面に積層された接着層15Aとを備える、第2積層体10Bを準備する。かかる第2積層体10Bは、貼り合わせ工程において、第1積層体10Aに貼り合わせられる。
支持層16は、接着層15Aと積層可能である層であれば特に限定されない。支持層16は、固体撮像素子1において何らかの機能を奏する機能層であるのが好ましい。
かかる機能層としては、保護層が挙げられる。保護層は、赤外吸収層15を化学的及び物理的に保護する層である。保護層の材料の好ましい具体例としては、酸化銀(I)(Ag2O)、一酸化銀(AgO)、酸化アルミニウム(Al2O3)、フッ化アルミニウム(AlF3)、フッ化バリウム(BaF2)、酸化セリウム(IV)(CeO2)、酸化クロム(III)(Cr2O3)、硫化クロム(III)(Cr2S3)、フッ化ガドリニウム(GdF3)、酸化ハフニウム(IV)(HfO2)、酸化インジウムスズ(ITO)、フッ化ランタン(LaF3)、ニオブ酸リチウム(LiNbO3)、フッ化マグネシウム(MgF2)、酸化マグネシウム(MgO)、ヘキサフルオロアルミン酸ナトリウム(Na3AlF6)、ご酸化ニオブ(Nb2O5)、ニッケルクロム合金(Ni-Cr)、ニッケルクロム合金の窒化物(NiCrNx)、窒酸化物(OxNy)、窒化シリコン(SiN4)、酸化シリコン(SiO)、に酸化シリコン(SiO2)、ご酸化タンタル(Ta2O5)、三酸化チタン(Ti2O3)、ご酸化チタン(Ti3O5)、酸化チタン(TiO)、二酸化チタン(TiO2)、酸化タングステン(WO3)、酸化イットリウム(Y2O3)、フッ化イットリウム(YF3)、硫化亜鉛(ZnS)、二酸化ジルコニウム(ZrO2)、及び酸化インジウム(In2O3)等が挙げられる。
支持層16が光反射防止層を含むと、反射光の再反射を低減できる。よって、反射光の再反射による撮像性能の低下を抑制することが可能となるという効果を奏する。
バンドパス層は、多層膜間の光の干渉を利用する。このため、入射光の入射角度によっては、バンドパス層を透過する透過光の波長がシフトする場合がある。このような場合であっても、透過波長のシフトが原理的に生じない近赤外吸収層15Bによって透過波長帯域が維持されることができるため、優れた撮像性能を維持できる。
第2積層体10Bの取り扱い性の点からは、支持層16が基材フィルムであるのが好ましい。
かかる硬化性組成物としては、(メタ)アクリレートモノマー、及びエチレン性不飽和二重結合を有する樹脂から選択される少なくとも1種と、硬化剤としての光又は熱重合開始剤とを含む組成物が挙げられる。
なお、本願明細書において、「(メタ)アクリル酸」は、アクリル酸とメタクリル酸との両方を意味する。同様に、「(メタ)アクリレート」は、アクリレートとメタクリレートとの両方を意味する。
典型的な例としては、フェノールノボラック型エポキシ化合物、臭素化フェノールノボラック型エポキシ化合物、オルソクレゾールノボラック型エポキシ化合物、キシレノールノボラック型エポキシ化合物、ナフトールノボラック型エポキシ化合物、ビスフェノールAノボラック型エポキシ化合物、ビスフェノールADノボラック型エポキシ化合物、ジシクロペンタジエン型フェノール樹脂のエポキシ化物、ナフタレン型フェノール樹脂のエポキシ化物等が挙げられる。
式(A1)で表されるエポキシ化合物の平均分子量は、1000以上が好ましく、1200以上がより好ましく、1500以上が特に好ましい。また、式(A1)で表されるエポキシ化合物の平均分子量は、50000以下が好ましく、20000以下がより好ましい。
アルキル基、アルコキシ基、脂肪族アシル基、脂肪族アシルオキシ基、及び不飽和脂肪族炭化水素基は、直鎖状であっても、分岐鎖状であってもよい。
アルキル基の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、及び2-エチルヘキシル基が挙げられる。
アルコキシ基の具体例としては、メトキシ基、エトキシ基、n-プロピルオキシ基、イソプロピルオキシ基、n-ブチルオキシ基、イソブチルオキシ基、sec-ブチルオキシ基、tert-ブチルオキシ基、n-ペンチルオキシ基、n-ヘキシルオキシ基、n-ヘプチルオキシ基、n-オクチルオキシ基、及び2-エチルヘキシルオキシ基が挙げられる。
2のRA1が結合して形成される環が複素環である場合、当該環に含まれるヘテロ原子としては、N、O、S、及びSe等が挙げられる。
2のRA1が結合することにより、ベンゼン環とともに形成される基の好適な例としては、ナフタレン環、及びテトラリン環が挙げられる。
2価の脂肪族環式基として、具体的には、モノシクロアルカン、ビシクロアルカン、トリシクロアルカン、テトラシクロアルカン等のポリシクロアルカンから2個の水素原子を除いた基等を例示できる。より具体的には、シクロペンタン、シクロヘキサン等のモノシクロアルカンや、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等のポリシクロアルカンから2個の水素原子を除いた基等が挙げられる。
2価の脂肪族環式基の炭素原子数は、3以上50以下が好ましく、3以上30以下がより好ましく、3以上20以下が特に好ましい。3以上15以下が最も好ましい。
芳香族炭化水素基を構成する芳香族炭化水素環の好適な具体例としては、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、及びターフェニルである。これらの芳香族炭化水素環から2+nc+nd個の水素原子を除いた基が、RA3としての芳香族炭化水素基として好適である。
RA4としてのハロゲン原子の好適な例としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。RA4としてのアルキル基の好適な例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、及びtert-ブチル基が好ましく、メチル基、及びエチル基がより好ましい。
式(A1-2)中のRA6は、ハロゲン原子、炭素原子数1以上4以下のアルキル基、又はフェニル基である。ハロゲン原子、及び炭素原子数1以上4以下のアルキル基の具体例については、RA4と同様である。
この場合、式(A1)で表されるエポキシ化合物に含まれる複数のエポキシ基の間に、適度な距離が存在することにより、より耐水性が良好な硬化物を形成しやすい。
これらの脂環式エポキシ化合物は単独で用いても2種以上混合して用いてもよい。
-L-Ca (a1-6a)
(式(a1-6a)中、Lは直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、-O-、-C(=O)-、-NH-及びこれらの組み合わせからなる基であり、Caはエポキシ基である。式(a1-6a)中、LとCaとが結合して環状構造を形成していてもよい。)
シロキサン化合物におけるシロキサン骨格としては、例えば、環状シロキサン骨格やかご型やラダー型のポリシルセスキオキサン骨格を挙げることができる。
また、-D-Ra27で表される脂環式エポキシ基含有基も好ましい。Ra27は、エポキシシクロアルキル基である。Dは前述の通り、アルキレン基である。Dとしてのアルキレン基の好ましい例も、前述の通りである。Ra27としてのエポキシシクロアルキル基としては、2,3-エポキシシクロペンチル基、3,4-エポキシシクロヘキシル基、及び2,3-エポキシシクロヘキシル基が好ましい。-D-Ra27で表される基としては、2-(3,4-エポキシシクロヘキシル)エチル基が好ましい。
オニウム塩は、露光、又は加熱によりエポキシ基を有する化合物を硬化させ得る。他のエポキシ用硬化剤は、加熱によりエポキシ基を有する化合物を硬化させ得る。
支持層16がごく薄かったり、支持層16の強度が低かったりする場合等には、基板上に支持層16を形成した後に、支持層16上に硬化性組成物を塗布し、次いで、塗布膜を所望する程度に乾燥させることにより支持層16上に接着層15Aを形成できる。
また、硬化性組成物の粘度を適切な範囲に調整したうえで、インクジェット法、スクリーン印刷法等の印刷法によって硬化性組成物の塗布を行ってもよい。
貼り合わせ工程では、図1に示されるように第1積層体10Aと、第2積層体10Bとを貼り合わせて、図2に示される第3積層体10Cを得る。図1に示されるように、第1積層体10Aと、第2積層体10Bとが貼り合わせられる際に、平坦化層14の表面と、接着層15Aの表面とが貼り合わせられる。
第1積層体10Aと、第2積層体10Bとを貼り合わせる方法は、特に限定されない。典型的には、貼り合わせられる面に均等に力を加えながら第1積層体10Aと、第2積層体10Bとが圧着される。貼り合わせを行う際には、第1積層体10A、又は第2積層体10Bが変形したり、熱により劣化したりしない程度の温度で第1積層体10A、又は第2積層体10Bが暖められてもよい。
硬化工程では、貼り合わせ工程後に、接着層15Aを、露光及び/又は加熱により硬化させて、接着層15Aと近赤外吸収層15Bとする。そうすることで、図3に示されるように、第3積層体10Cが、固体撮像素子1となる。
加熱を行う際の温度は特に限定されず、100℃以上280℃以下が好ましく、120℃以上260℃以下がより好ましく、140℃以上250℃以下が特に好ましい。加熱時間は、典型的には、1分以上60分以下が好ましく、2分以上50分以下がより好ましく、5分以上40分以下が特に好ましい。
また、以上の方法により、平坦化層14の表面を、有機溶剤により荒らすことなく固体撮像素子を製造できる。
ここでは、保護層を用いる場合について説明したが、上記の方法により、固体撮像素子1において、種々の機能層を近赤外吸収層15Bの表面に積層出来る。
積層体は、固体撮像素子1において近赤外吸収層15Bを形成するために好適に用いられる。
かかる積層体は、支持層16と、支持層16の一方の面に積層された接着層15Aとを備える。接着層15Aは、硬化性化合物と、近赤外吸収化合物とを含む。硬化性化合物は、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物である。
つまり、上記の積層体は、前述の第2積層体に該当する。
ドライフィルムは、固体撮像素子1において近赤外吸収層15Bを形成するために好適に用いられる。
かかるドライフィルムは、基材フィルムと、基材フィルムの一方の面に積層された接着層15Aとを備える。接着層15Aは、硬化性化合物と、近赤外吸収化合物とを含む。硬化性化合物は、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物である。
つまり、上記のドライフィルムは、前述の支持層16として基材フィルムを備える前述の第2積層体に該当する。
Claims (9)
- 光電変換層を備える、第1積層体を準備する、第1積層体準備工程と、
支持層と、前記支持層の一方の面に積層された接着層とを備える、第2積層体を準備する、第2積層体準備工程と、
前記第1積層体と、前記第2積層体とを貼り合わせて第3積層体を得る、貼り合わせ工程と、
前記貼り合わせ工程後に、前記接着層を露光及び/又は加熱により硬化させて前記接着層を近赤外線吸収層とする、硬化工程と、を含み、
前記第1積層体が、光電変換層と、前記光電変換層上のカラーフィルター層と、前記カラーフィルター層上のレンズと、前記レンズを被覆する平坦化層とを備え、
前記接着層が、硬化性化合物と、近赤外吸収化合物とを含み、
前記硬化性化合物が、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物であり、
前記第3積層体において、前記平坦化層の表面と、前記接着層の表面とが貼り合わせられている、固体撮像素子の製造方法。 - 前記近赤外吸収化合物が、スクアリリウム化合物、ジイモニウム化合物、シアニン化合物、フタロシアニン化合物、及び銅錯体からなる群より選択される1種以上である、請求項1に記載の固体撮像素子の製造方法。
- 前記硬化性化合物が、(メタ)アクリレートモノマー、及びエチレン性不飽和二重結合を有する樹脂から選択される少なくとも1種を含み、前記接着層が前記硬化剤として光又は熱重合開始剤を含む、請求項1又は2に記載の固体撮像素子の製造方法。
- 前記硬化性化合物が、エポキシ基を有する化合物を含み、前記接着層が前記硬化剤としてエポキシ用硬化剤を含む、請求項1又は2に記載の固体撮像素子の製造方法。
- 前記第2積層体準備工程において、前記支持層上に、前記硬化性化合物、前記近赤外吸収化合物、及び溶媒を含む硬化性組成物を塗布して塗布膜を形成し、次いで、塗布膜から前記溶媒の少なくとも一部を除去して前記接着層を形成する、請求項1~4のいずれか1項に記載の固体撮像素子の製造方法。
- 前記支持層が、保護層である、請求項1~5のいずれか1項に記載の固体撮像素子の製造方法。
- 前記支持層が、前記接着層から剥離可能な基材フィルムであり、
前記貼り合わせ工程後に、前記接着層から前記基材フィルムを剥離させ、前記基材フィルムの剥離により露出した前記接着層の面に保護層を貼り合わせ、
前記保護層を前記接着層に貼り合わせた後に、前記接着層硬化工程を行う、請求項1~5のいずれか1項に記載の固体撮像素子の製造方法。 - 支持層と、前記支持層の一方の面に積層された接着層とを備え、
前記接着層が、硬化性化合物と、近赤外吸収化合物とを含み、
前記硬化性化合物が、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物である、
固体撮像素子において近赤外線吸収層を形成するために用いられる積層体。 - 基材フィルムと、基材フィルムの表面に形成された接着層とを備え、
前記接着層が、硬化性化合物と、近赤外吸収化合物とを含み、
前記硬化性化合物が、硬化剤の作用により、又は硬化剤の作用によらず露光及び/又は加熱により硬化する化合物であり、
前記基材フィルムが、前記接着層から剥離可能である、
固体撮像素子において近赤外線吸収層を形成するために用いられる、ドライフィルム。
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