JP2013042123A - 研磨剤及び基板の研磨方法 - Google Patents
研磨剤及び基板の研磨方法 Download PDFInfo
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- JP2013042123A JP2013042123A JP2012156809A JP2012156809A JP2013042123A JP 2013042123 A JP2013042123 A JP 2013042123A JP 2012156809 A JP2012156809 A JP 2012156809A JP 2012156809 A JP2012156809 A JP 2012156809A JP 2013042123 A JP2013042123 A JP 2013042123A
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- polishing
- abrasive
- layer
- cobalt
- acid
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Abstract
【解決手段】フタル酸化合物、イソフタル酸化合物及び下記一般式(I)で表されるアルキルジカルボン酸化合物並びにこれらの塩及び酸無水物からなる群より選択される少なくとも1種からなるカルボン酸誘導体と、金属防食剤と、水とを含有し、pHが4.0以下である、コバルト元素を含む層を研磨するための研磨剤である。一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。
HOOC−R−COOH・・・(I)
【選択図】なし
Description
<1> フタル酸化合物、イソフタル酸化合物及び下記一般式(I)で表されるアルキルジカルボン酸化合物並びにこれらの塩及び酸無水物からなる群より選択される少なくとも1種からなるカルボン酸誘導体と、金属防食剤と、水とを含有し、pHが4.0以下である、コバルト元素を含む層を研磨するための研磨剤である。
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。)
このような研磨剤とすることによって、コバルト層に対する良好な研磨速度を保ちながら、腐食抑制性を向上させることができる。
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。)
このような研磨剤とすることによって、コバルト層に対する良好な研磨速度を保ちながら、腐食抑制性を向上させることができる。
これにより、腐食性をより効果的に抑制することができる。
これにより、被研磨膜がコバルト層以外の層を含む場合に、コバルト層以外の層の研磨速度をより向上させることができる。
これにより、被研磨膜がコバルト層以外の層を含む場合に、コバルト層以外の層に対する濡れ性が向上するため、研磨速度をより向上させることができる。
これにより、被研磨面が保護されて腐食を抑制し、傷等のディフェクト発生を低減することができる。
これにより、被研磨膜がコバルト層以外の層を含む場合に、コバルト層以外の層の研磨速度をより向上させることができる。
本発明の研磨方法によれば、コバルト元素を含む被研磨膜を高速にかつ過度な腐食を抑制しつつ研磨することが可能となる。
本発明の研磨剤は、フタル酸化合物、イソフタル酸化合物及び下記一般式(I)で表されるアルキルジカルボン酸化合物並びにこれらの塩及び無水物からなる群より選択される少なくとも1種からなるカルボン酸誘導体と、金属防食剤と、水とを含有し、pHが4.0以下である。
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。)
本発明の研磨剤は、フタル酸化合物、イソフタル酸化合物及び上記一般式(I)で表されるジカルボン酸化合物(以下、これらを「特定ジカルボン酸化合物」ともいう)並びにこれらの塩及び酸無水物からなる群より選択される少なくとも1種であるカルボン酸誘導体(以下、「特定カルボン酸誘導体」ともいう。)を含む。前記特定カルボン酸誘導体は、1種類単独で、もしくは2種類以上混合して用いることができる。無数に存在するカルボン酸及びカルボン酸誘導体の中から、前記特定カルボン酸誘導体を選択することにより、コバルト層に対する良好な研磨速度を保ちながら、適度にエッチング速度が制御されて腐食が抑制され、良好な研磨面を得ることができる。更により厳しい条件下(例えば50℃)であっても、コバルト層のエッチング速度がより効果的に抑制され、優れた腐食抑制性が達成できる。ここで腐食抑制性に優れるとは、被研磨面において、コバルト層がエッチングされたり、配線層にスリットが生じたりすることが効果的に抑制されることを含む。
本発明の研磨剤に含まれる金属防食剤としては特に制限はなく、金属に対する防食作用を有する化合物として従来公知のものがいずれも使用可能である。具体的には、トリアゾール化合物、ピリジン化合物、ピラゾール化合物、ピリミジン化合物、イミダゾール化合物、グアニジン化合物、チアゾール化合物、テトラゾール化合物、トリアジン化合物、ヘキサメチレンテトラミンから選択される少なくとも1種を用いることができる。ここで「化合物」とは、その骨格を有する化合物の総称であり、例えばトリアゾール化合物とはトリアゾール骨格を有する化合物を意味する。
前記カルボン酸誘導体と、トリアゾール化合物、ピリジン化合物、イミダゾール化合物、テトラゾール化合物、トリアジン化合物及びヘキサメチレンテトラミンからなる群より選択される少なくとも1種の金属防食剤との比率(カルボン酸誘導体/金属防食剤)が5/1〜1/5であることがより好ましく、
前記カルボン酸誘導体と、3H−1,2,3−トリアゾロ[4,5−b]ピリジン−3−オール、1−ヒドロキシベンゾトリアゾール、1H−1,2,3−トリアゾロ[4,5−b]ピリジン、ベンゾトリアゾール等のトリアゾール化合物、3−ヒドロキシピリジン、ベンズイミダゾール、5−アミノ−1H−テトラゾール、3,4−ジヒドロ−3−ヒドロキシ−4−オキソ−1,2,4−トリアジン及びヘキサメチレンテトラミンからなる群より選ばれる少なくとも1種の金属防食剤との比率(カルボン酸誘導体/金属防食剤)が5/1〜1/1であることが更に好ましい。
前記研磨剤は、少なくとも1種の酸化剤を更に含むことが好ましい。酸化剤を更に含むことでコバルト層以外の層の研磨速度をより向上させることができる。前記酸化剤は、特に制限はなく、通常用いられる酸化剤から適宜選択することができる。具体的には、過酸化水素、ペルオキソ硫酸塩、硝酸、過ヨウ素酸カリウム、次亜塩素酸、オゾン水等が挙げられ、中でも過酸化水素が好ましい。これら金属酸化剤は、1種類単独で又は2種類以上を混合して用いることができる。
前記研磨剤は、さらに有機溶剤が含まれてもよい。有機溶剤の添加により、コバルト層の近傍に設けられたコバルト層以外の層の濡れ性を向上させることができ、研磨速度をより向上させることができる。前記有機溶剤としては、特に制限はないが、水溶性のものが好ましい。ここで水溶性とは、水100gに対して25℃において0.1g以上溶解するものとして定義される。
前記研磨剤は、少なくとも1種の水溶性ポリマーを含むことが好ましい。これにより、腐食効果の抑制、膜表面の保護、ディフェクト発生の低減等がより効果的に達成できる。ここで水溶性とは、25℃において、水100gに対して0.1g以上溶解するものとして定義される。
試料:10μL
標準ポリアクリル酸:日立化成テクノサービス株式会社製 商品名:PMAA−32
検出器:株式会社日立製作所製、RI−モニター、商品名「L−3000」
インテグレーター:株式会社日立製作所製、GPCインテグレーター、商品名「D−2200」
ポンプ:株式会社日立製作所製、商品名「L−6000」
脱気装置:昭和電工株式会社製、商品名「Shodex DEGAS」
カラム:日立化成工業株式会社製、商品名「GL−R440」、「GL−R430」、「GL−R420」をこの順番で連結して使用
溶離液:テトラヒドロフラン(THF)
測定温度:23℃
流速:1.75mL/分
測定時間:45分
前記研磨剤は、少なくとも1種の砥粒を含むことが好ましい。砥粒を含むことで、コバルト層の近傍に設けられたコバルト層以外の層の研磨速度を向上させることができる。
本発明で用いられる水は、特に制限されるものではないが、純水を好ましく用いることができる。水は前述した研磨剤の構成材料の残部として配合されていればよく、含有量は特に制限はない。
前記研磨剤に添加できるその他の成分としては、例えば、界面活性剤、ビクトリアピュアブルー等の染料、フタロシアニングリーン等の顔料などの着色剤が挙げられる。
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。)
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。)
本発明の基板の研磨方法は、基板の少なくとも一方の表面に形成されたコバルト元素を含む被研磨膜を、前述した研磨剤を用いて研磨して、コバルト元素を含む余分の部分を除去する研磨方法である。より具体的には、基板の少なくとも一方の表面に形成されたコバルト元素を含む被研磨膜と研磨定盤上の研磨布との間に、前述した研磨剤を供給しながら、前記被研磨膜が設けられた面側の前記基板表面を研磨布に押圧した状態で、該基板と研磨定盤とを相対的に動かすことによって被研磨膜の少なくとも一部を除去する研磨方法である。
研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂等が使用でき、特に制限はない。
[実施例及び比較例]
(研磨剤作製方法)
容器に、表1及び表2に示す金属防食剤及びカルボン酸誘導体を、最終的な研磨剤として表1に記載の配合量となるようにそれぞれ入れ、水溶性ポリマーとしてポリアクリル酸アンモニウム塩(日立化成テクノサービス製、分子量8000)を最終的な研磨剤として0.02質量%となる量、有機溶剤として3−メトキシ−3−メチル−1−ブタノールを最終的な研磨剤として1.4質量%となる量を入れ、そこに超純水を注ぎ、攪拌・混合して、全成分を溶解させた。
得られた各研磨剤のpHを測定し、表1及び表2に示した。
8インチのシリコン基板上にCVD法で厚さ300nmのコバルト層を形成したブランケット基板(a)を用意した。上記ブランケット基板(a)を、20mm角のチップに切り出して評価用チップ(b)を用意した。
浸漬後のコバルト層の膜厚[nm]
=104.5×(評価用チップ(b)の抵抗値[mΩ]/1000)−0.893
・・・(1)
コバルト層のエッチング速度(Co−ER)[nm/min]
=(浸漬前のコバルト層の膜厚[nm]―浸漬後のコバルト層の膜厚[nm])/1分
・・・(2)
また、上記ブランケット基板(a)を、上記で得られた各研磨剤を用いて、下記条件で研磨したときの研磨速度(Co−RR)[nm/min]を評価した。この結果を表1及び表2に併せて示す。尚、比較例いくつかについては、エッチング速度が速すぎたため、研磨速度の評価を省略し、「−」で表記した。
研磨布:IC1000
研磨圧力:10.3kPa(1.5psi)
回転数:プラテン/ヘッド=93/87rpm
研磨剤の供給量:200mL/分
研磨時間:0.5分
2 絶縁体
3 バリア金属層
4 コバルト層
5 導電性物質層(配線用金属)
Claims (8)
- フタル酸化合物、イソフタル酸化合物及び下記一般式(I)で表されるアルキルジカルボン酸化合物並びにこれらの塩及び酸無水物からなる群より選択される少なくとも1種からなるカルボン酸誘導体と、金属防食剤と、水とを含有し、pHが4.0以下である、コバルト元素を含む層を研磨するための研磨剤。
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。) - フタル酸化合物、イソフタル酸化合物及び下記一般式(I)で表されるアルキルジカルボン酸化合物並びにこれらの塩及び酸無水物からなる群より選択される少なくとも1種のカルボン酸誘導体と、金属防食剤と、水とを含有し、pHが4.0以下であり、50℃におけるコバルトに対するエッチング速度が10.0nm/min以下である、コバルト元素を含む層を研磨するための研磨剤。
HOOC−R−COOH・・・(I)
(上記一般式(I)中、Rは炭素数が4〜10であるアルキレン基を示す。) - 前記金属防食剤はトリアゾール骨格を有する化合物を含有する請求項1又は請求項2に記載の研磨剤。
- 更に酸化剤を含有する請求項1〜請求項3のいずれか1項に記載の研磨剤。
- 更に有機溶剤を含有する請求項1〜請求項4のいずれか1項に記載の研磨剤。
- 更に水溶性ポリマーを含有する請求項1〜請求項5のいずれか1項に記載の研磨剤。
- 更に砥粒を含有する請求項1〜請求項6のいずれか1項に記載の研磨剤。
- 基板の少なくとも一方の表面に形成されたコバルト元素を含む被研磨膜を、請求項1〜請求項7のいずれか1項に記載の研磨剤を用いて研磨して、コバルト元素を含む余分な部分を除去する基板の研磨方法。
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JP7028592B2 (ja) | 2017-09-19 | 2022-03-02 | 株式会社フジミインコーポレーテッド | 表面処理組成物、表面処理組成物の製造方法、表面処理方法、および半導体基板の製造方法 |
JP2020183481A (ja) * | 2019-05-08 | 2020-11-12 | 花王株式会社 | 酸化珪素膜用研磨液組成物 |
JP7209583B2 (ja) | 2019-05-08 | 2023-01-20 | 花王株式会社 | 酸化珪素膜用研磨液組成物 |
WO2021101227A1 (ko) * | 2019-11-21 | 2021-05-27 | 엘티씨 (주) | 디스플레이 제조용 포토레지스트 박리액 조성물 |
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JP6051632B2 (ja) | 2016-12-27 |
KR101846607B1 (ko) | 2018-04-06 |
KR20130011943A (ko) | 2013-01-30 |
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