TWI460232B - 倍半矽氧烷樹脂 - Google Patents
倍半矽氧烷樹脂 Download PDFInfo
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- C08G77/04—Polysiloxanes
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Description
本發明係關於一種適用於抗反射塗層中之倍半矽氧烷樹脂。
隨著半導體工業對較小特徵尺寸之持續需求,最近已出現193mm光學微影術技術作為製造次-100nm特徵之器件的技術。利用此較短波長之光需要底層抗反射塗層(BARC)以降低基板上的反射且藉由吸收已穿過光阻之光以抑制光阻擺動固化。可購得之抗反射塗層(ARC)係由有機及無機材料組成。通常而言,顯示良好抗蝕性之無機ARC係CVD基且易具有極端拓撲學之所有積體化缺點。有機ARC材料係藉由旋壓法施加且具有極佳填充與平坦化性質,但對有機光阻的蝕刻選擇性較差。因此,強烈需要能提供無機與有機ARC材料組合優勢之材料。
本發明係關於適用於抗反射塗層中之倍半矽氧烷樹脂,其中該倍半矽氧烷樹脂具有化學式(PhSiO(3-x)/2
(OR')x
)m
(HSiO(3-x)/2
(OR')x
)n
(MeSiO(3-x)/2
(OR')x
)o
(RSiO(3-x)/2
(OR')x
)p
(R2
SiO(3-x)/2
(OR')x
)q
其中Ph係苯基;Me係甲基;R係選自含硫有機官能基;R'係氫原子或具有1至4個碳原子之烴基;R2
係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且。當抗反射塗層中使用該等樹脂時,可在去除階段脫除該塗層。此外,對作爲193nm ARC材料之所需固化性質及脫除能力,倍半矽氧烷樹脂中必需存在氫原子基團。
本發明亦有關於抗反射塗層(ARC)組合物,其包括:
(i)具有化學式(PhSiO(3-x)/2
(OR')x
)m
(HSiO(3-x)/2
(OR')x
)n
(MeSiO(3-x)/2
(OR')x
)o
(RSiO(3-x)/2
(OR')x
)p
(R2
SiO(3-x)/2
(OR')x
)q
之倍半矽氧烷樹脂
其中Ph係苯基;Me係甲基;R係選自含硫有機官能基;R'係氫原子或具有1至4個碳原子之烴基;R2
係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且;及
(ii)一溶劑。
本發明亦有關一種在電子器件上形成抗反射塗層之方法,其包括:
(A)將ARC組合物施加在電子器件上,該組合物包括
(i)具有化學式(PhSiO(3-x)/2
(OR')x
)m
(HSiO(3-x)/2
(OR')x
)n
(MeSiO(3-x)/2
(OR')x
)o
(RSiO(3-x)/2
(OR')x
)p
(R2
SiO(3-x)/2
(OR')x
)q
之倍半矽氧烷樹脂
其中Ph係苯基;Me係甲基;R係選自含硫有機官能基;R'係氫原子或具有1至4個碳原子之烴基;R2
係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且;及
(ii)一溶劑,且去除溶劑且固化倍半矽氧烷樹脂以在電子器件上形成抗反射塗層。
適用於形成抗反射塗層中之倍半矽氧烷樹脂具有化學式(PhSiO(3-x)/2
(OR')x
)m
(HSiO(3-x)/2
(OR')x
)n
(MeSiO(3-x)/2
(OR')x
)o
(RSiO(3-x)/2
(OR')x
)p
(R2
SiO(3-x)/2
(OR')x
)q
其中Ph係苯基;Me係甲基;R係選自含硫有機官能基;R'係氫原子或具有1至4個碳原子之烴基;R2
係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且。通常m值為0.02至0.7,或者0.05至0:15。通常n值為0.05至0.90,或者0.10至0.30。通常o值為0.05至0.90,或者0.25至0.75。通常p值為0.02至0.20,或者0.05至0.5。通常q值為0至0.25,或者0至0.15。
在樹脂中,R係含硫官能基。R可藉由具有通式HS(CH2
)z
-(其中z值為1至18)之氫硫基烷基、具有通式R3
S(CH2
)z
-、R3
SS(CH2
)z
-及R3
SSS(CH2
)z
-(其中R3
係H原子)之硫化物或多硫基化合物、C1-C4烷基諸如甲基、乙基或丙基或芳基諸如苯基例示。R可進一步藉由氫硫基丙基、氫硫基乙基及氫硫基甲基例示。
R'獨立為氫原子或具有1至4個碳原子之烴基。R'可藉由H、甲基、乙基、丙基、異丙基及丁基例示。
R2
係選自酯基團、聚醚基團及聚氧化乙烯基團。酯基團可為任何包含至少一個酯官能性之有機取代基。聚醚基團為具有經由氧原子連接之烴基單元之有機取代基,可由下列化學表示,但不限於:-(CH2
)a
[O(CH2
)b
]c
OR',其中a=2至12;b=2至6;c=2至200;R'=H、烷基或其他有機基團。聚氧化乙烯基團為具有至少一個重複單元-(CH2
CH2
O)t-之基團,其中t係選自0至50之數字。文中適用之酯基團實例係-(CH2
)2
-O-C(O)Me及-(CH2
)2
-C(O)-OMe。文中適用之聚醚基團實例係-(CH2
)3
-(OCH2
CH2
)7
-OMe、-(CH2
)3
-(OCH2
CH2
)7
-OH及-(CH2
)3
-(OCH2
CH2
)7
-OAc。文中適用之聚氧化乙烯實例係-(CH2
)3
-(OCH2
CH2
)t
-OMe、-(CH2
)3
-(OCH2
CH2
)t
-OC(O)Me及-(CH2
)3
-(OCH2
CH2
)t
-OH。
製造倍半矽氧烷樹脂之常用方法係涉及適合矽烷之水解及縮合。藉由此方法,由於不完全水解或縮合,倍半矽氧烷樹脂中可能殘留殘基-OH及/或OR'。若倍半矽氧烷樹脂中包含-OR'基團之單元總量超過40莫耳%,則樹脂可能出現凝膠化及不穩定。通常倍半矽氧烷樹脂包含小於5莫耳%之含-OR'基團之單元,或者小於1莫耳%。
倍半矽氧烷樹脂具有利用RI檢測及聚苯乙烯標準藉由凝膠滲透層析術所測得在500至50,000範圍內,或者在2500至25,000範圍內,或者在4,000至20,0000範圍內之重量平均分子量(Mw)。
倍半矽氧烷樹脂可藉由此項技術中已知之方法製得。例如,其等可利用屬於Becker等人之美國專利第6,281285號及屬於Bank等人之美國專利第5,010,159號中闡述之方法,藉由三氯矽烷之水解及縮合製得。或者,倍半矽氧烷樹脂可經由烷氧基矽烷之水解及縮合製得。
通常,在溶劑的存在下製造倍半矽氧烷樹脂。任何適宜之不含有可參與水解及/或縮合反應之官能基團之有機或矽酮溶劑皆可用於製造倍半矽氧烷樹脂。溶劑一般係以基於溶劑與矽烷反應物總重量之40至98重量%(或者70至90重量%)之量使用。該反應可以雙相或單相系統進行。
適用有機溶劑可藉由(但不限於)飽和脂族諸如正-戊烷、己烷、正庚烷及異辛烷;環脂族諸如環戊烷及環己烷;芳香族諸如苯、甲苯、二甲苯、均三甲苯;醚諸如四氫呋喃、二噁烷、乙二醇二***、乙二醇二甲醚;酮諸如甲基異丁基酮(MIBK)及環己酮;經鹵素取代之烷烴諸如三氯乙烷;鹵化芳香族諸如溴苯及氯苯;酯諸如丙二醇單甲醚乙酸酯(PGMEA)、異丁酸異丁酯及丙酸丙酯例示。適用矽酮溶劑可藉由(但不限於)環狀矽氧烷諸如八甲基環四矽氧烷及十甲基環五矽氧烷例示。可使用單一溶劑或使用溶劑混合物。
製造倍半矽氧烷樹脂之反應可在任何溫度下進行,只要其不引起明顯凝膠化或引起倍半矽氧烷樹脂固化。通常而言,反應係在5℃至150℃範圍內(建議在50℃至100℃範圍內)之溫度下進行。
形成倍半矽氧烷樹脂之時間係取決於許多因素諸如溫度、矽烷反應物的類型及用量及觸媒量(若存在)。反應時間通常係從幾分鐘至幾小時。熟習此項技術者將能輕易判定完成反應之所需時間。可用於加速反應之觸媒包括,但不限於硝酸、硫酸、鹽酸及其他物。
完成反應後,視需要可去除觸媒。去除觸媒之方法在此項技術中係熟知的且包括中和、脫除或水洗或其組合。觸媒可能對矽酮樹脂之儲存壽命,尤其係在溶液中時有負面影響,因此建議將其去除。
在製造倍半矽氧烷樹脂之方法中,完成反應後,在降低壓力下可將揮發成份從倍半矽氧烷樹脂溶液中去除。該等揮發成份包括醇副産物、過量水、觸媒、鹽酸(氯矽烷路線)及溶劑。去除揮發成份之方法在此項技術中係已知的且包括(例如)蒸餾。
製造倍半矽氧烷樹脂之反應後,視需要可進行多個步驟以獲得所需形式之倍半矽氧烷樹脂。例如,倍半矽氧烷樹脂可經由去除溶劑以固體形式回收。溶劑去除之方法並非關鍵且大量方法在此項技術中係熟知的(例如,加熱及/或真空蒸餾)。一旦以固體形式回收倍半矽氧烷樹脂,則可視需要將樹脂重新溶解於相同或另一溶劑中以供特定使用。或者,若最終産物需要不同溶劑(異於反應中所用之溶劑),則可藉由添加二次溶劑及例如經由蒸餾去除第一溶劑而完成溶劑交換。此外,溶劑中樹脂濃度可藉由去除一些溶劑或添加附加量之溶劑作調整。
本發明亦係關於抗反射塗層(ARC)組合物,其包括
(i)具有化學式(PhSiO(3-x)/2
(OR')x
)m
(HSiO(3-x)/2
(OR')x
)n
(MeSiO(3-x)/2
(OR')x
)o
(RSiO(3-x)/2
(OR')x
)p
(R2
SiO(3-x)/2
(OR')x
)q
之倍半矽氧烷樹脂
其中Ph係苯基;Me係甲基;R係選自含硫有機官能基;R'係氫原子或具有1至4個碳原子之烴基;R2
係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且;及
(ii)一溶劑。
適用溶劑(ii)尤其包括但不限於1-甲氧基-2-丙醇、丙二醇單甲基乙基乙酸酯及環己酮。ARC組合物通常包含基於ARC組合物總重量之約10重量%至約99.9重量%(或者80至95重量%)之溶劑。
ARC組合物可包含自由基引發劑或其他添加劑。適宜自由基引發劑包括過氧化物及光引發劑諸如過氧化苯甲醯、過氧化二異丙苯、偶氮雙異丁腈(AIBN)及其他物。自由基引發劑通常係以基於ARC組合物總重量之至多1000ppm(或者10至500ppm)之量存在。其他添加劑可包括,但不限於光-酸及熱-酸産生劑、光-鹼及熱-鹼産生劑。
抗反射塗層組合物係藉由混合倍半矽氧烷樹脂、溶劑及視需要自由基引發劑或其他添加劑所形成。自由基引發劑或其他添加劑通常係在其使用之前才加入塗層組合物中以阻止提前固化。
將抗反射塗層組合物施加在電子器件上以産生經塗布之基板。去除溶劑且固化倍半矽氧烷樹脂以在電子器件上産生抗反射塗層。
電子器件通常為半導體器件,諸如欲用於製造半導體組件之矽基器件及砷化鎵基器件。通常,器件包含至少一個半導電性層及多個其他包含各種導電性、半導電性或絕緣性材料之層。
施加ARC組合物於電子器件之具體方法包括,但不限於旋塗、浸塗、噴塗、淋塗、網版印刷及其他方法。較佳施加方法係旋塗。通常,塗布涉及在約2000RPM下旋轉電子器件且將ARC組合物添加至旋轉電子器件的表面上。
去除溶劑且在電子器件上固化倍半矽氧烷樹脂以形成抗反射塗層。固化一般包括將塗層加熱至一足夠溫度達一足夠時間以令其固化。當足夠交聯以致倍半矽氧烷樹脂基本上不溶於施加其之溶劑時,發生固化。例如,藉由在80℃至450℃下加熱經塗布電子器件達0.1至60分鐘、或者在150℃至275℃下0.5至5分鐘,或者在200℃至250℃下0.5至2分鐘進行固化。在固化步驟期間可使用任何加熱方法。例如,可將經塗布電子器件放置在石英管爐、對流烘箱中或令放置在加熱板上。或者,抗反射塗層可在光活性添加劑(諸如光-酸産生劑(PAG)或光鹼産生劑)之存在下經紫外線照射而固化。
為防止固化期間塗層組合物之倍半矽氧烷樹脂與氧或碳反應,固化步驟可在惰性氛圍下進行。文中適用之惰性氛圍包括,但不限於氮氣及氬氣。「惰性(inert)」意指環境包含小於50ppm,較佳係小於10ppm之氧氣。進行固化及去除步驟之壓力並非關鍵。固化步驟通常係在大氣壓力下進行,但亦可在真空壓力或超大氣壓力進行。
一旦固化,包含抗反射塗層之電子器件可用於另外基板加工步驟諸如光學微影術中。當用於光學微影術中時,抗蝕圖像在抗反射塗層上形成。形成抗蝕圖像之方法包括(a)在抗反射塗層頂部形成抗蝕組合物薄膜;(b)使抗蝕薄膜圖像化地暴露於輻射中以製造曝光薄膜;及(c)使曝光薄膜顯影産生圖像。電子器件上之抗反射塗層尤其適合利用圖像化地暴露於波長為157nm至365nm之紫外線輻射,或者波長為157nm或193nm之紫外線輻射中之抗蝕組合物。抗蝕薄膜中圖像一旦産生,則圖案就被蝕刻在抗反射塗層中。可利用已知蝕刻材料以去除抗反射塗層。可利用附加步驟或去除抗蝕薄膜及殘留抗反射塗層以製造具有所需結構之器件。
ARC塗層組合物可在較低溫度下固化且其等産生可經脫除溶液去除之塗層。已發現文中製造之抗反射塗層具有較佳溶劑(例如PGMEA)及TMAH抗性。
包含下列實例以說明本發明之實施例。熟習此項技術者應暸解依照本發明者所揭示之代表技術之實例中所揭示之技術可在本發明之實施中發揮作用,因此被認為組成其較佳實施模型。然而鑑於本發明,熟習此項技術者應暸解在所揭示之具體實施例中可做很多改變且仍獲得相似或類似結果而未背離本發明之精髓與範圍。
包含下列實例以說明本發明之較佳實施例。熟習此項技術者應暸解依照本發明者所揭示之代表技術之實例中所揭示之技術可在本發明之實施中發揮作用,因此被認為組成其較佳實施模型。然而鑑於本發明,熟習此項技術者應暸解在所揭示之具體實施例中可做很多改變且仍獲得相似或類似結果而未背離本發明之精髓與範圍。所有百分比皆係重量%。
反應物之使用量係列於表1中。在氮氣下,將PGMEA、苯基三氯矽烷(矽烷1)、三氯矽烷(矽烷2)、甲基三氯矽烷(矽烷3)與2-(甲氧羰基)乙基三氯矽烷(矽烷4)及氫硫基丙基三甲氧基矽烷(矽烷5)之混合物加入一反應器中。在90分鐘內,將PGMEA與水之溶液加入三氯矽烷溶液中。使反應稠化且20℃下再攪拌1小時。所得反應産物係經水或水/乙基乙酸酯清洗且分離。然後於樹脂溶液中加入乙醇且溶液係經脫除至約22重量%。然後於溶液中加入冷正己烷且收集底層。加入附加PGMEA且溶液係經脫除至PGMEA中具<10重量%固體。該溶液係經附加PGMEA稀釋至10重量%。溶液經由0.20微米PTFE過濾器過濾。製得通式為T(H)T(Me)T(Ph)T(R2
)T(R)之樹脂。結果係列於表2中。試驗4/5係以一次試驗形式進行且産物係經分離而獲得兩種不同Mw之樹脂。
Claims (22)
- 一種具下式之倍半矽氧烷樹脂:(PhSiO(3-x)/2 (OR')x )m (HSiO(3-x)/2 (OR')x )n (MeSiO(3-x)/2 (OR')x )o (RSiO(3-x)/2 (OR')x )p (R2 SiO(3-x)/2 (OR')x )q ,其中Ph係苯基;Me係甲基;R係式HS(CH2 )z -之氫硫基烷基基團,其中z值為1至18,或R3 SS(CH2 )z -之多硫基團,其中R3 係H原子、C1-C4烷基或芳基,其中z值為1至18;R'係氫原子或具有1至4個碳原子之烴基;R2 係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且m+n+o+p+q1。
- 如請求項1之倍半矽氧烷樹脂,其中m值為0.02至0.7,n值為0.05至0.90,o值為0.05至0.90,p值為0.02至0.20且q值為0至0.25。
- 如請求項1之倍半矽氧烷樹脂,其中R係氫硫基丙基基團。
- 如請求項1之倍半矽氧烷樹脂,其中R2 係選自酯基團、聚醚基團及聚氧化乙烯基團。
- 如請求項1之倍半矽氧烷樹脂,其中R2 係-(CH2 )2 -C(O)-OMe。
- 如請求項1之倍半矽氧烷樹脂,其中該樹脂具有在500至50,000範圍內之分子量。
- 一種抗反射塗層組合物,其包括: (i)具下式之倍半矽氧烷樹脂:(PhSiO(3-x)/2 (OR')x )m (HSiO(3-x)/2 (OR')x )n (MeSiO(3-x)/2 (OR')x )o (RSiO(3-x)/2 (OR')x )p (R2 SiO(3-x)/2 (OR')x )q 其中Ph係苯基;Me係甲基;R係式HS(CH2 )z -之氫硫基烷基基團,其中z值為1至18,或R3 SS(CH2 )z -之多硫基團,其中R3 係H原子、C1-C4烷基或芳基,其中z值為1至18;R'係氫原子或具有1至4個碳原子之烴基;R2 係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且m+n+o+p+q1;及(ii)一溶劑。
- 如請求項7之抗反射塗層組合物,其中m值為0.02至0.7,n值為0.05至0.90,o值為0.05至0.90,p值為0.02至0.20,且q值為0至0.25。
- 如請求項7之抗反射塗層組合物,其中R係氫硫基丙基基團。
- 如請求項7之抗反射塗層組合物,其中R2 係選自酯基團、聚醚基團及聚氧化乙烯基團。
- 如請求項7之抗反射塗層組合物,其中R2 係-(CH2 )2 -C(O)-OMe。
- 如請求項7之抗反射塗層組合物,其中該樹脂具有在500至50,000範圍內之分子量。
- 如請求項7之抗反射塗層組合物,其中該溶劑係選自1-甲 氧基-2丙醇、丙二醇單甲基乙基乙酸酯及環己酮。
- 如請求項7之抗反射塗層組合物,其中該組合物另外包含自由基引發劑。
- 一種在電子器件上形成抗反射塗層之方法,其包括(A)將ARC組合物施加在電子器件上,該組合物包括(i)具下式之倍半矽氧烷樹脂:(PhSiO(3-x)/2 (OR')x )m (HSiO(3-x)/2 (OR')x )n (MeSiO(3-x)/2 (OR')x )o (RSiO(3-x)/2 (OR')x )p (R2 SiO(3-x)/2 (OR')x )q 其中Ph係苯基;Me係甲基;R係式HS(CH2 )z -之氫硫基烷基基團,其中z值為1至18,或R3 SS(CH2 )z -之多硫基團,其中R3 係H原子、C1-C4烷基或芳基,其中z值為1至18;R'係氫原子或具有1至4個碳原子之烴基;R2 係選自酯基團、聚醚基團及聚氧化乙烯基團;x值為0、1或2;m值為0.01至0.97;n值為0.01至0.97;o值為0.01至0.97;p值為0.01至0.97;q值為0至0.96;且m+n+o+p+q1;及(ii)一溶劑;以及(B)去除溶劑且固化倍半矽氧烷樹脂以在電子器件上形成抗反射塗層。
- 如請求項15之方法,其中R係氫硫基丙基基團。
- 如請求項15之方法,其中R2 係-(CH2 )2 -C(O)-OMe。
- 如請求項15之方法,其中該溶劑係選自1-甲氧基-2-丙醇、丙二醇單甲基乙基乙酸酯及環己酮。
- 如請求項15之方法,其中該組合物另外包含自由基引發 劑。
- 如請求項15之方法,其中該ARC組合物係藉由旋塗、浸塗、噴塗、淋塗或網版印刷施加。
- 如請求項15之方法,其中該倍半矽氧烷樹脂係藉由在80℃至450℃下加熱0.1至60分鐘而固化。
- 如請求項21之方法,其中該倍半矽氧烷樹脂係在惰性氛圍中加熱。
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- 2008-12-05 CN CN200880124283.3A patent/CN101910255B/zh not_active Expired - Fee Related
- 2008-12-05 US US12/811,130 patent/US8318258B2/en not_active Expired - Fee Related
- 2008-12-05 JP JP2010542226A patent/JP5587791B2/ja not_active Expired - Fee Related
- 2008-12-05 EP EP08869497A patent/EP2240534B1/en not_active Not-in-force
- 2008-12-18 TW TW097149444A patent/TWI460232B/zh active
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Also Published As
Publication number | Publication date |
---|---|
WO2009088600A1 (en) | 2009-07-16 |
US20120027917A1 (en) | 2012-02-02 |
EP2240534A4 (en) | 2011-11-16 |
US8318258B2 (en) | 2012-11-27 |
JP5587791B2 (ja) | 2014-09-10 |
JP2011509333A (ja) | 2011-03-24 |
EP2240534B1 (en) | 2013-01-23 |
CN101910255B (zh) | 2013-07-10 |
CN101910255A (zh) | 2010-12-08 |
KR20100126295A (ko) | 2010-12-01 |
EP2240534A1 (en) | 2010-10-20 |
TW200938591A (en) | 2009-09-16 |
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