TW200428525A - Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film - Google Patents
Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film Download PDFInfo
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- TW200428525A TW200428525A TW093111948A TW93111948A TW200428525A TW 200428525 A TW200428525 A TW 200428525A TW 093111948 A TW093111948 A TW 093111948A TW 93111948 A TW93111948 A TW 93111948A TW 200428525 A TW200428525 A TW 200428525A
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- ferroelectric
- thin film
- liquid composition
- ferroelectric thin
- particles
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0036—Mixed oxides or hydroxides containing one alkaline earth metal, magnesium or lead
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
-
- 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
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Description
200428525 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關形成強介電體薄膜用液狀組成物及利用 其製造強介電體薄膜之方法者。 【先前技術】 近來’做爲新型記憶體元件受矚目之強介電體記憶體 (FeRAM )係積極利用強介電體薄膜之自發分極特性後, 進行情報之讀取’因此,被期待於揮發性、書寫速度、信 賴性、單位面積等面可有效克服目前尙存之DRAM、 SRAM ' FLASH記憶體等缺點,開發一種理想之記憶體 者。 做爲FeRAM用之強介電體材料者目前爲止有鈸酸鉻 酸鉛系(PZT PLZT )、鉍系層狀鈣鈦礦強介電體 (BLSF)等金屬氧化物系材料被提出硏討之。 通常,此等強介電體薄膜被揭示有藉由濺射法等物理 生氣相成膜法(PVD ) 、MOCVD法等化學性氣相成長 法、及化學性溶液成膜法(溶液法)進行成膜方法者。其 中,溶液法於公知者係無需特殊之高價裝置下,可以最廉 價且簡便下進行強介電體薄膜之成膜者。又,溶液法易於 控制精社、之組成’出現於多數強介電體材料,具有依不同 組成可抑制特性變動之優點,做爲一種極有效之強介電體 薄S吴製造方法之一被積極討論之。 藉由溶液法製作強介電體薄膜係於基板上進行塗佈均 -5- (2) (2)200428525 質溶解原料之各成份金屬化合物(前驅物)溶液後,使塗 膜乾燥後,必要時進行煅燒(pre-bake )後,於空氣中以 約7〇〇°C或更高溫度下進行燒成後形成結晶性金屬氧化物 薄膜後,進行強介電體薄膜之成膜方法者。做爲原料之可 溶性金屬化合物者通常使用金屬烷氧化物,其部份水解物 或有機酸鹽、螯合絡合化合物之有機金屬化合物者。 另外,針對使用該FeR AM之單位構造目前有幾個單 位構造被揭示之,惟,現行實用化者以局部配線連接強介 電體電容器與晶體管,所謂葡萄石構造者,其單位面積之 縮小化,亦即,高集成化之觀點視之爲不利構造者。 做爲解決此等構造者,被揭示有於管塞所形成強介電 體電容器之通風構造者,惟,於多層配線形成時,其還原 氣氛引起強介電體薄膜致命的劣化特性之問題點。更做爲 解決此等問題之結構者被揭示有進行多層配線之形成後, 亦即結束邏輯程序後,於最上層形成強介電體薄膜與平板 線之構造者。此構造中爲做成對於理論電路上之成膜,於 強介電體薄膜形成時之燒成溫度被要求降至400°C〜450°C 者。 爲對應此,有關藉由溶液法之強介電體薄膜之製作中 亦降低結晶化溫度之各種方法被揭示之。如:USP 5 59 2 5 ,183公報等所示之適當控制前驅物構造之方法,預 先將常介電體之矽酸鉍力Π入塗層液之方法 (Ferroelectrics,271 卷,289 頁(2002 年)),以鈦酸 鉛層做爲晶種層使用之方法(J P n . J . A p p 1. P h y s ; 3 5卷, -6 - (3) (3)200428525 4896 頁 (1996 年)),適當基材之選擇 (J.Am.Ceram.Soc.,75 卷,2785 頁(1992 年))’滅壓锻 燒法(Jpn· J.Appl.Phys.,38 卷,5346 頁( 1999 年)等 者。惟,此等先行方法中燒成溫度均降至5 5 0 °C爲極限 者。因此,藉由溶液法時’事實上對於形成高集成化必要 理論電路上之強介電體薄膜者極爲不易者。 更且,嘗試使用強介電體之微粒子與可溶性金屬鹽共 存之組成物形成薄膜者(Jpn.J.Appl.Phys.,41卷,6969頁 (2 002年))。惟,此強介電體之微粒子係使用藉由長 時間機械性粉碎取得之粒子者,因此,將導致降低粒子之 結晶性,而未能取得所期待之特性。 【發明內容】 本發明鑑於上述先行技術之問題點,而提供一種以溶 液法進行成膜後取得強誘電體薄膜時,於較低溫度下,特 是 5 5 0 °C以下,甚至4 5 0 °C以下之溫度可進行燒成,因 此,可於高集成化對於必要之理論電路上形成強介電體薄 膜,且,可製作具有耐電壓、自發分極性,特別是疲勞特 性等面具良好之強誘電體特性薄膜之形成薄膜用液狀組成 物,及使用其之製造強介電體薄膜之方法爲目的者。 本發明持續進行精密硏討後達成該目的,其特徵爲具 有下記構成者。 (1 )液狀媒體中以一般式AB〇3 ( A爲至少1種選自 Ba2+、Sn2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,B 爲 -7- (4) (4)200428525 至少1種選自Ti4+、Zr4+、Nb5+、Ta5+及Fe3+所成群 者。)所示之具有鈣鈦礦構造,平均一次粒徑爲10 Onm 以下者,且,形態比爲2以上之板狀或針狀結晶之強介電 體氧化物粒子被分散之’且’溶解藉由加熱後形成強介電 體氧化物之可溶性金屬化合物者爲其特徵之形成強介電體 薄膜用液狀組成物者。 (2 )可溶性金屬化合物係藉由加熱後,形成一般式 AB〇3 ( A 爲至少一種選自、Ba2+、Sr2+、Ca2+、Pb2+、 La2+、K+及 Na+所成群者,B爲至少一種選自 Ti4+、 Zr4+、Nb5+、Ta5 +及Fe3 +所成群者。)所示之具有鈣鈦礦 構造之強介電體氧化物之化合物者之該(1 )所載形成強 介電體薄膜用液狀組成物。 (3 )強介電體氧化物粒子係於玻璃基質中使強介電 體氧化物粒子進行結晶化後去除玻璃基質成份後取得之粒 子之該(1 )或(2 )所載形成強介電體薄膜用液狀組成 (4 )含強介電體氧化物粒子/可溶性金屬化合物之比 率以氧化物換算之質量比下,5/95〜95/5之該(1 )〜(3 ) 中任一項之形成強介電體薄膜用液狀組成物。 (5 )含強介電體氧化物粒子與可溶性金屬化合物之 總量爲1〜5 0質量%之(1 )〜(4 )中任一項之形成強介電 體薄膜用液狀組成物。 (6 )於基板上塗佈該(1 )〜(5 )中任一項之液狀組 /¾¾ ‘後’ Μ 5 5 G°C以下進行燒成之製造強介電體薄膜之方 冬 (5) (5)200428525 法。 (7 )強介電體薄膜之膜厚爲10〜3 00nm者之(6 )所 介電體薄膜之製造方法。 【實施方式】 [發明實施之最佳形態] &下,針對本發明進行詳細說明。 本發明中一般式AB〇3 ( A爲至少1種選自 Ba2+、 St2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,B 爲至少 1 種選自Ti4+、Zr4+、Nb5+、Ta5 +及Fe3 +所成群者。)所示 之具鈣鈦礦構造之強介電體氧化物結晶粒子(以下亦簡稱 強介電體粒子)係做爲本發明組成物中根幹之必須成份 者。本發明中藉由使用分散具該高結晶性之強介電體粒子 於液狀媒體之液狀組成物後,於目前溶液法所使用之可溶 性金屬化合物溶液進行成膜時,可飛躍性降低必要之燒成 溫度。 該強介電體粒子爲具有一般式AB〇3 ( A,B爲與上述 相同者)所示之1¾欽礦構造之強介電體者,該一般式之A 以Ba2+、Sr2+、Pb2 +者宜,B以Ti4+、Zr4 +者宜。其中又 以A爲Pb、B爲Ti與Zr之複合氧化物者之Pb (ZrxTi】 -x ) 03 ( X爲〇·1〜0.9者。以下亦稱PZT。)者 宜。當然,此ΡΖΤ之Pb定位以其他元素,如La等稀土 類元素做爲部份取代之PLZT之公知的強介電體等亦可使 用之。 冬 (6) (6)200428525 該強介電體粒子其平均一次粒徑務必爲l〇〇nm以下 者。其中,以一次粒徑之長徑爲基準,又’平均粒徑爲數 平均粒徑者。當平均一次粒徑大於此時’則薄膜形成時袠 面之凹凸變粗,薄膜中之塡充率不提昇,介電特性降低。 其中又以平均一次粒徑爲50nm以下者較佳,特別以 10〜30nm爲最佳。當平均一次粒徑不足l〇nm則粒子之強 介電特性將降低。 本發明強介電體粒子,具該範圍平均一次粒徑之同 時,更且,其形態爲各向異性結晶粒子,亦即,其形態比 務必爲2以上之板狀或針狀結晶者。其中,形態比係指具 有各向異性粒子之長徑/短徑比率者,板狀結晶者爲直徑/ 厚度之比率、針狀結晶者爲長度/直徑之比率者。特別 是,本發明錦欽礦型之強介電體氧化物中,自發分極方向 與結晶格子之C軸方向多半爲一致者,例如··垂直於c 軸之面(〇 〇 1 )面)使用成長之板狀結晶後,其塗佈後粒 子自發性整列於c軸方向,亦即,容易定位,具取得高度 自發分極値之優點。且,可提昇強介電體粒子之定位性, 因此連帶的亦提昇強介電體薄膜之疲勞特性。本發明中形 態比小於2時,則將降低所形成強介電體薄膜之特性而不 理想。當形態比爲5以上時爲最理想者。 做爲具有該特性之強介電體粒子者,特別由具有高度 結晶性者’於玻璃基質中使強誘電體粒子結晶化後去除玻 璃基質成份之後取得之粒子者宜。亦即,於玻璃母材融液 中溶解做爲強誘電體粒子被結晶化之成份後放置之,融液 - 10- (7) (7)200428525 進行急速冷卻後玻璃化後,再度進行加熱煅燒後母材中藉 由析出微結晶之玻璃結晶化法後取得之粒子者。所析出之 微結晶藉由適當藥液等溶解玻璃基質後被取出。 於該玻璃基質中被結晶化之超微粒子易於控制形態、 煅燒處理之條件等較易製作各向異性較大之微粒子,同時 亦具有易於取得形態比大的粒子之優點。 做爲該玻璃母材者一般可使用硼酸系、磷酸系、砂酸 系等,而,由熔融性,易與目的氧化物複合化合物製造、 基質溶離之容易性等面觀之,又以硼酸系之玻璃母材爲較 佳使用者。 以下’強介電體氧化物粒子之製造以製作鈦酸鉻酸鉛 (PZT )微結晶之方法爲例進行具體之說明後,可於以下 ①〜④步驟取得強介電體粒子。 ① 混合玻璃形成成份(如氧化硼)與做爲目的之強介 電體氧化物粒子組成金屬氧化物(如氧化鉻、氧化鈦及氧 化鉛)後,整體於120(TC以上之溫度下進行熔融[熔融]。 ② 使熔融玻璃進行急速冷卻後,取得含強介電體氧化 物組成金屬離子之玻璃[玻璃化]。 ③ 於5 5 0 °C〜7 0 0 °C之溫度下進行椴燒處理後,玻璃中 形成強介電體氧化物之結晶核、控制煅燒條件後,使成長 至所定粒徑爲止[結晶化]。 ④ 藉由其酸、水或其混合物取得去除玻璃母材成份 (如:氧化硼)之強介電體粒子(如,
Pb ( ΖγχΊΠ】·χ ) 03 )[瀝濾]。 (8) (8)200428525 藉由上記一連串步驟,於煅燒溫度範圍下,以極高粘 度之玻璃做爲母材進行結晶化,因此,極易控制強介電體 粒子之粒徑、粒子形態,且可取得高結晶性之微結晶者。 另夕丨’本發明中藉由加熱可形成強介電體氧化物之可 溶性金屬化合物(以下亦稱可溶性金屬化合物)係指藉由 加熱之熱分解等轉化成氧化物後顯示強介電性之化合物 者。做爲目的之強介電體氧化物爲複合氧化物時,可使用 以所定比率混合2種以上可溶性金屬化合物者,或於所定 比例含2種以上金屬之複合金屬化合物使用之。做爲此等 可溶性金屬化合物者可使用硝酸鹽等無機酸鹽、乙基己烷 酸鹽、乙醯丙酮絡合物等有機金屬絡合物、或金屬烷氧化 物等’特別以有機酸鹽、有機金屬絡合物、或金屬烷氧化 物爲較佳使用者。 由本發明強介電體薄膜形成用液狀組成物形成強介電 體薄膜之過程中,該可溶性金屬化合物具有做爲強介電體 氧化物結晶粒子之結合劑作用,此可溶性金屬化合物可以 前述強介電體粒子做爲核進行結晶成長者,可由更低溫形 成結晶化者。又,可溶性金屬化合物於熱處理之燒成後, 於強介電體粒子間之空隙中形成強介電體氧化物後,亦具 有提昇做爲整體強介電體薄膜之介電特性作用者。 該可溶性金屬化合物亦可具有於燒成後形成與強介電 體粒子略同組成之強介電體之組成者,亦可具有形成不同 於強介電體粒子組成之強介電體之組成者。惟,考量該強 介電體粒子做爲結晶核作用時,又以形成可達強介電體粒 -12- 200428525 Ο) 子之相同組成的強介電體者爲較佳者。 本發明中含強介電體粒子與可溶性金屬化合物之比率 係於可溶性金屬化合物加熱後呈氧化物時之氧化物換算質 量比下,其強介電體粒子/可溶性金屬化合物比率爲 5/9 5〜9 5/5者宜。當此強介電體粒子大於此範圍時,則結 合劑成份將不足,而所形成薄膜恐無法密合於基板,反 之’小於該範圍時,將不易出現強介電體粒子之添加效 果。其中該比率做成3 0 / 7 0以上時,則可提昇強介電體粒 子之定向性,易取得高特性之強介電體薄膜爲特別理想 者。反之’該比率做成70/3 0以下則較易取得密緻之強介 電體薄膜爲理想者。 該強介電體粒子與可溶性金屬化合物係於適當之液狀 媒體中分散強介電體粒子,且,做爲溶解可溶性金屬化合 物之液狀組成物者使用強介電體薄膜形成用之塗佈液等 等。形成該液狀組成物時,亦可混合強介電體粒子與可溶 性金屬鹽化合物後於液狀媒體中進行溶解或分散之,亦可 分別於相同或相異之液狀媒體中分散或溶解者進行混合 之。做爲液狀媒體者只要可溶解可溶性金屬化合物者即 可,無特別限定,通常可使用水、醇(乙醇、2 —丙醇 等)、醚醇(2 —乙氧基乙醇、2—乙氧基丙醇等)、醋 (醋酸丁酯、乳酸乙酯等)、酮(丙酮、甲基異丁酮 等)、醚(二丁醚、二氧陸圜等)、脂肪族烴基(環己 烷、癸烷等)、芳香族烴基(甲苯、二甲苯)、含氮有機 溶媒(乙腈、N -甲基吡咯烷酮等)、或此等之2種以上 -13- (10) (10)200428525 混合溶媒者。做爲具體之液狀媒體者可依其組成物中之結 晶粒子之種類,表面狀態,可溶性金屬化合物之種類,更 依其塗佈方法進行適當選取、混合使用之。又,液狀媒體 中亦可含部份可溶性金屬化合物之未溶解份者。 做爲本發明液狀組成物中固形份(強介電體粒子與可 溶性金屬化合物之合計)之含量可依其目的之強介電體膜 厚、液狀物之塗佈方法等進行適當調節,一般以1〜5 0質 量%者宜。當小於該範圍時其藉由塗佈取得薄膜之厚度將 變得極小,爲取得所期待之厚度將務必重覆極多次之塗 佈,反之,大於該範圍時,則恐降低液的安定性。 又’本發明形成液狀組成物之該強介電體粒子,媒體 中溶解或分散可溶性金屬鹽化合物時,可使用球磨器、混 砂機,等媒體硏磨器、超音波式、攪拌式等各種勻漿器、 注射硏磨器、滾輥硏磨器等已知之方法、裝置者。 本發明液狀組成物中亦可含有爲分散該強介電體粒 子、可溶性金屬化合物之分散劑、爲改善塗膜之液流學特 性等之各種界面活性劑、表面處理劑、樹脂成份等。惟, 此等大量添加後於燒成後易呈殘碳份殘留之,因此以必要 最小限之量進行添加爲宜。 基板上塗佈本發明液狀組成物後,進行燒成後可製造 強介電體薄膜。做爲塗佈方法者,可使用己知之方法者。 理想之具體例如:旋轉塗佈法、浸瀆塗佈法、噴霧塗佈 法、濾網印刷法、複製印刷法等例。其中又以旋轉塗佈法 其取得薄膜之均質性、生產性面爲最理想者。 -14 - (11) (11)200428525 做爲本發明形成薄膜時所使用之基板者如:Si、GaAs 等單結晶半導體基板、BaTi〇3、SrTi〇3、MgO、A1203等 之單結晶介電體基板,於此等表面上堆積多結晶Si,做爲 電極層者堆積Pt、Ir、Ir〇2、RU、Rll〇2等者,或於半導體 基板與該電極層之間設置Si02、Si3N4等之絕緣層Ti、Ta 之緩衝層者。惟,做爲基板者只要具有燒成溫度之耐熱性 者即可,不受限於此等。 於此等基板上塗佈本發明液狀組成物後,較佳者爲去 除媒體,一般於1 0 0〜4 0 0 °c下進行乾燥1分鐘至2小時 後,進行燒成之。此燒成係於如上述之本發明中可採用低 溫範圍者,理想者爲5 5 0 °C以下,依情況於4 5 0 °C以下進 行之。當然燒成亦可採用超過550 °C之溫度者,不同用途 下該®溫亦有利燒成者。燒成時間依其溫度,氣氛而異, 一般以1分鐘至2小時進行之。此燒成係使可溶性金屬化 合物進行分解及/或結晶化者,適當選於大氣中,氧、不 活性氣體下等進行使用之。燒成中亦可使用擴散爐類之電 爐’使用可急速昇溫之熱感光板、紅外線燈煅燒爐 (RTA )等後,更易進行結晶化較爲理想者。 如上述,形成本發明之強介電體薄膜時,使膜厚以 1〇〜3〇〇nm考宜。當膜厚不足l〇nm時,則不易取得均質 膜者’反之,超出3〇〇nm時,則恐於膜中出現裂化而不 里…、为外’由塗佈一乾燥一燒成所成之一次步驟中無法 取得所期待之膜厚時,當然可重覆進行此步驟。 列舉以下實施例進行本發明具體之說明,惟,本發明 -15- (12) (12)200428525 未受限於以下實施例。又,例6〜例8爲比較例者。 [例強介電體粒子(PZT)之製作] $氧化鉛、氧化鉻、氧化鈦(金紅石),及氧化硼秤 取含PbO、Zr〇2、Ti02及B2〇3者分別爲47.2莫耳%、 1 3 . 3莫耳%、n · 7莫耳%、及2 7 · 8莫耳%後,使用少量乙 酉亭&自動乳鉢充份濕式混合乾燥之後做成原料粉末。所取 ί辱原、Μ粉末塡充於融液滴入用噴嘴所附之鉑製容器(含 1〇%錄)後’以矽化鉬做爲發熱體之電爐中1 3 5 0 °C下進行 加熱2小時後,完全熔融之。再加熱噴嘴部位後,將融液 設置於電爐下之雙滾輥(滾輥經1 5 0mm、滾輥旋轉數 5〇rpm '滚輥表面溫度3〇艺)中滴入後取得碎片狀固形 物。 所取得碎片狀固形物確定呈透明狀,粉末x線衍射 之結果’爲非晶質物質者。此碎片狀固形物於5〇(rc下加 熱12小時後’ B2〇3玻璃基質中顯示強介電體粒子出現結 晶化者。再使該碎片粉加入維持於8〇〇C2 Imol/L醋酸水 溶液中攪梓6小時後,進行離心分離、水洗淨、乾燥之 後’取得白色粉末。 取得白色粉末藉由粉末χ線衍射後進行固定之後, 判定爲Pb ( zr〇.52 Ti G 48) 〇3結晶所成之粉末者。又,Zr 與Tx之比率依ICP法進行定量之。又,藉由透光型電子 顯微鏡進行觀察後結果此結晶呈板狀形,平均一次粒徑 2 0 n m,厚度爲9 n m,形態比爲2 · 2 2者。 -16- (13) (13)200428525 [例2 —強介電體粒子BaTi〇3之製作] 使碳酸鋇、氧化鈦(金紅石)、及氧化硼秤取B aO、 T i Ο 2、及B 2 0 3分別爲5 〇 · 〇、1 6.7、及3 3 . 3莫耳%後,使 用少量乙醇’以自動乳鉢充份進行濕式混合乾燥後做成原 料粉末。將取得原料粉末塡入附融液滴入用噴嘴之鉑製容 器(含1 〇%錢)後,矽化鉬於做爲發熱體之電爐中於 1 3 5 0 °C下加熱2小時後,完全熔融之。再加熱噴嘴部位 後,於電爐下方設置之雙滾輥(滾輥徑1 5 0 m m、滾輥旋 轉數50rpm、滾輥表面溫度30°C )中滴入融液後,取得碎 片狀固形物。 取得碎片狀固形物確定呈透明狀,粉末X線衍射之 結果爲非晶質物質者。此碎片狀固形物於5 9 0 °C下加熱1 2 小時後,進行結晶化處理。再將此碎片粉加入維持8 〇 之]m ο 1 / L之醋酸水溶液中,攪拌1 2小時後,進行離心分 離、水洗淨、乾燥之後,取得白色粉末。 藉由粉末X線衍射同定取得白色粉末後,證明爲金太 酸鋇結晶所成之粉末者。又,藉由透光型電子顯微鏡進行 觀察之結果,此結晶爲板狀形,平均一次粒徑爲2 5 n m, 厚度爲1 〇 η π),形態比爲2 · 5 0者。 [例3 - ΡΖΤ強介電體薄膜之製作] 利用濕式噴射硏磨器使例I取得之ΡΖΤ結晶粒子分 散於乙醇中,藉由離心分離後,去除粗大粒子,取得含 - 17- (14) (14)200428525 1 0質量%之PZT分散液A。利用激光散射粒度分佈計測定 該分散液A之分散粒徑後爲90nm者’呈良好之分散體。 使醋酸鉛、四丁基鈦酸酯、四丁基鉻酸酯及乙醯丙酮 於 2 —乙氧基丙醇中呈 Pb: Zr: Ti: Z醯丙酮=1·05: 0.5 3 : 0.4 7 : 1 : 00 (莫耳比)溶解之,氮氣流中130°C下 進行4小時迴流操作。將此溶液冷卻至室溫後,緩緩加入 離子交換水呈(Pb + Zr + Ti )之2倍(莫耳比)。之後,再 度於氮氣流中,1 3 0 °C下進行8小時迴流加熱後,取得可 溶性金屬化合物溶液B。另外,金屬源之液中濃度以氧化 物換算成1〇質量%者。 分散液A與可溶性金屬化合物溶液B以質量比(氧 化物換算値)混合呈5 0/5 0後,做成本發明組成物。 做爲基板者使用於表面層合Pt層(厚度200nm) /Ti 層(厚度20nm) /熱氧化3丨02層(厚度8 00nm)之聚矽氧 單結晶基板後,藉由旋轉塗佈法該組成物塗佈於表面之 Pt層後,於熱感光板上20 (TC下進行乾燥30分鐘。進行 此塗佈一乾燥處理3次之後,利用PTA爐於氧中45 下 進行燒成3 0分鐘。 取得被膜爲厚度1 OOnm,X線衍射結果優先定位於C 軸方向之PZT結晶相所成之被膜者。更於此被膜上藉由 DC濺射法製作〇.imm 0之pt電極,於pta爐40(TC,進 行1 5分鐘之後煅燒處理製作電容器後,測定強介電體滯 後特性之後,抗電界値爲44kV/cm,自發分極値爲 3 5pC/cm2者。取得強介電體電容器之疲勞特定之評定 -18- (15) (15)200428525 (循環試驗中,自發分極降低初期之5 %以上循環數) 後,重覆進行3V、108次循環後自發分極値之變化量仍控 制於5 %以內。 [例4] 利用濕式噴射硏磨器將例2取得之BaTi03結晶粒子 分散於乙醇後,藉由離心分離去除粗大粒子’取得含10 質量%之BaTi03分散液C。利用激光散射粒度分佈計測定 該分散液C之分散粒徑後爲8 0 n m之良好分散體者。 使金屬鋇、四丁基鈦酸酯、及二乙二醇溶於2 -甲氧基 丙醇中呈Ba: Ti:二乙二醇=1: 1: 1(莫耳比),於氮氣 流1 1 (TC下進行迴流操作4小時後’冷卻至室溫,使離子交 換水呈(Ba + Ti )之2倍(莫耳比)緩緩進行添加之。隨 後,再度於氮氣流1 1 〇°C下進行迴流加熱8小時後,取得可 溶性金屬化合物溶液D。另外,金屬源之液中濃度以氧化物 換算爲10質量%者。 使分散液C與可溶性金屬化合物溶液D呈質量比(氧 化物換算)70/30進行混合後,做成本發明組成物。 以表面層合 Pt層(厚度200n m) /Ti層(厚度 20n m) /熱氧化Si02層(厚度800nm)之聚砂氧單結晶基 板做爲基板使用後,於表面Pt層上藉由旋轉塗佈法進行 塗佈該組成物後,於熱感光板2 00 °C下進行乾燥30分 鐘。此塗佈一乾燥之處理進行3次後,利用RTA爐於氧 中5 0 0 °C下進行燒成2 0分鐘。 -19- (16) (16)200428525 取得被膜其厚度爲1 2 0 n m,X線衍射之結果,優先定 向於C軸方向之BaTi03結晶相所成之被膜。更於此被膜 上藉由DC濺射法製作〇.imm 0之Pt電極。於RTA爐 4 5 0 °C下進行後椴燒處理1 5分鐘後,製造電容器後測定強 介電體滯後特性之後,抗電界値爲30kv/cm,自發分極値 爲19pC/cm2。與例3同法進行評定取得強介電體電容器 之疲勞特性後,重覆± 3 V、1 06次之循環後仍可控制自發 分極値之變化量為約5 %者。 [例5〜7] 使用含1 〇質量%固相法下所製成之一次平均粒徑 1 ·2μηι (形態比1 )之球狀PZT結晶粒子分散液E取代例 3之強介電體結晶分散液Α後與例3同法進行成膜/評 定。取得相由 PZT單相所成之強介電體相者,分極特性 亦與例3取得之被膜爲相等者,惟,疲勞特性之評定中其 3 V,1 06次循環下之自發分極幾乎呈零,明顯出現劣化 者。另外,X線衍射之結果’強介電體相爲無定向者。 [例9] 利用行星式球磨器使固相法下所製成之球狀ΡΖΊΓ粒 子(平均一次粒徑1 ·2 ym )進行粉碎4 0小時。電子顯微 1¾觀察結果’粒徑爲微細化至4 0 n m考。利用此微粉末取 代例3之強介電體結晶分散液A,與例3之分散液a同法 進行調製分散液後,與例3同法製作pZT被膜。取得之 (17) 200428525 相爲PZT單相所成之強介電體相者,而,藉由粉碎後出 現ΡΖΤ結晶之變形影響。或自發分極値變小,且,疲勞 特性於1〇6次之循環下之自發分極亦降至初期之50%者。 另外,X線衍線之結果,強介電體相爲無定向者。 [表1]
例 結晶粒子 (a) 平均一次粒 子徑(nm) 形態比 可溶性金屬化 合物(b) 組成物中U) / (b)質量比 燒成溫度 例3 例1之PZT 20 2.22 PZT Zr/Ti=53/47 50/50 450〇C 例4 例2之BT 25 2.50 BT 70/30 500°C 例5 例1之PZT 20 2.22 PZT Zr/Ti=53/47 66/34 450〇C 例6 例1之PZT 25 2.22 PZT Zr/Ti=53/47 80/20 450〇C 例‘7 — 一 — PZT Zr/Ti=53/47 0/100 450〇C 例8 PZT 1200 1 PZT Zr/Ti=53/47 50/50 450〇C 例9 PZT 粉碎品 40 — PZT Zr/Ti=53/47 50/50 450〇C
-21 - (18) 200428525 [表 2] 例 膜厚(ηηι) 結晶相 抗電界 自發分極 疲勞特性 (kV/cm) (pC/cm2) (循環) 例3 100 PZT單相 44 35 >1〇8 例4 120 BT單相 30 19 -106 例5 100 PZT單相 49 39 >108 例6 100 PZT單相 51 39 >108 例7 110 非晶質 _ 例8 115 PZT單相 48 29 <104 例9 100 PZT單相 35 12 <104
[產業上可利用性] 本發明係提供一種,以溶液法進行成膜後,取得強介 電體薄膜時,於較低溫,特別是5 5 0 °C以下,更於4 5 0 °C 以下之溫度下可進行燒成,因此,可形成高集成所須理論 電路上之強介電體薄膜,且,具有良好抗高電性、自發分 極性、特別是可製造出疲勞特性均良好之強介電體特性薄 膜之薄膜形成組成物,及使用其製造強介電體薄膜之方法 者。 由本發明所製造之強介電體薄膜可有效做爲記憶元件 及其他裝置製造之使用。特別是膜厚爲丨〇〜300nm時,可期 待適用於FeRAM者。 -22-
Claims (1)
- 200428525 Π) 拾、申請專利範圍 1. 一種形成強介電體薄膜用液狀組成物,其特徵係 t 於液狀媒體中分散具有一般式AB〇3 ( A爲至少一種選自 、 Ba2+、Sr2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,b 爲 至少一種選自Ti4+、Zr4+、Nb5+、Ta5 +及Fe3 +所成群者) 所示之鈣鈦礦構造,其平均一次粒徑爲100nm以下, 且,形態比爲2以上之板狀或針狀結晶之強介電體氧化物 粒子’同時溶解藉由加熱形成強介電體氧化物之可溶性金 φ 屬化合物者。 2· ‘如申請專利範圍第1項之形成強介電體薄膜用液 狀組成物,其中該可溶性金屬化合物係藉由加熱後形成具 有一般式 AB〇3 ( A代表至少一種選自 Ba2+、Sr2+、 Ca2+、Pb2+、La2+、K +及Na +所成群者,B代表至少一種 選自Ti4+、Zr4+、Nb5+、Ta5 +及Fe3 +所成群者)所示之鈣 欽礦構造之強介電體氧化物之化合物者。 3 ·如申請專利範圍第1項或第2項之形成強介電體薄 馨 膜用液狀組成物,其中該強介電體氧化物粒子係使強介電 體氧化物粒子於玻璃基質中結晶化後去除玻璃基質後,取 得之粒子者。 4. 申請專利範圍第1項至第3項中任一項之形成強介 · 電體薄膜用液狀組成物,其中該強介電體氧化物粒子/可溶 - 性金屬化合物之含有比率以氧化物換算之質量比爲 5/9 5 〜9 5/5 者。 5. 如申請專利範圍第1項至第4項中任一項之形成強 -23- (2) (2)200428525 介電體薄0吴用液狀組成物’其中該強介電體氧化物粒子與可 溶性金屬化合物之總計含量爲1〜50質量%者。 6 · —種強介電體薄膜之製造方法,其特徵係使如申請 專利範圍第1項至第5項中任一項之液狀組成物塗佈於基 板上,於5 5 0 °C以下之溫度下進行燒成者。 7.如申請專利範圍第6項之強介電體薄膜之製造方 法,其中該強介電體薄膜之膜厚爲10〜300nm者。-24 - 200428525 柒、(一)、本案指定之代表圖為:無 (二)、本代表圖之元件代表符號簡單說明:無 捌、本案若有化學式時,請揭示最能顯示發明特徵的化學式:
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