JP4811556B2 - 圧電素子、液体噴射ヘッドおよび液体噴射装置 - Google Patents
圧電素子、液体噴射ヘッドおよび液体噴射装置 Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims description 16
- 239000013078 crystal Substances 0.000 claims description 59
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 58
- 238000004458 analytical method Methods 0.000 claims description 49
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 44
- 238000009792 diffusion process Methods 0.000 claims description 41
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- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 16
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- 229910052726 zirconium Inorganic materials 0.000 claims description 11
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- 238000006243 chemical reaction Methods 0.000 claims description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 102100029860 Suppressor of tumorigenicity 20 protein Human genes 0.000 description 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
- B08B9/027—Cleaning the internal surfaces; Removal of blockages
- B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
- B08B9/0321—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing using pressurised, pulsating or purging fluid
- B08B9/0328—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing using pressurised, pulsating or purging fluid by purging the pipe with a gas or a mixture of gas and liquid
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14201—Structure of print heads with piezoelectric elements
- B41J2/14233—Structure of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
- H01L28/65—Electrodes comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
- H10B53/30—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors characterised by the memory core region
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
- H10N30/078—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition by sol-gel deposition
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/005—Details of cleaning machines or methods involving the use or presence of liquid or steam the liquid being ozonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2209/00—Details of machines or methods for cleaning hollow articles
- B08B2209/005—Use of ultrasonics or cavitation, e.g. as primary or secondary action
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
- H01L27/10—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration
- H01L27/105—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration including field-effect components
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- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Semiconductor Memories (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Formation Of Insulating Films (AREA)
Description
さらに、本発明の目的は、上記強誘電体膜積層体を用いた圧電素子、液体噴射ヘッドおよびプリンタを提供することにある。
前記PZT系強誘電体膜は、Bサイト(Nb,Ti組成)のうち、2.5モル%以上40モル%以下をNbに置換し、
前記電極は、前記PZT系強誘電体膜から拡散する酸素をほぼ含まない。
x+y+z=1、
0≦x≦0.975
が成立する。
前記PZT系強誘電体膜は、Bサイトのうち、2.5モル%以上40モル%以下をNbに置換し、
前記PZT系強誘電体膜は、該PZT系強誘電体膜における酸素原子の割合の分布がほぼ一定である。
図1は、本発明の実施形態に係る強誘電体膜積層体を適用した強誘電体キャパシタ100を模式的に示す断面図である。
x+y+z=1、
0≦x≦0.975
が成立する。
本実施例では、本願発明によるPZTNと従来のPZTとを比較する。成膜フローは全て前述の図2を用いた。
本実施例では、PZTN強誘電体膜において、Nb添加量を0、5、10、20、30、40モル%と変化させて強誘電特性を比較した。全ての試料においてPbSiO3シリケートを5モル%添加している。また、膜形成のための原料となる強誘電体膜形成用ゾルゲル溶液には、コハク酸ジメチルを添加してpHを6とした。成膜フローは全て前述の図2を用いている。
本実施例では、例えば、強誘電体メモリのメモリセル部分を構成する強誘電体キャパシタや例えば、インクジェットプリンターのインク吐き出しノズル部分を構成する圧電アクチュエータの電極材料として用いられるPtやIrなどの白金系金属からなる金属膜上にPZTN膜を形成した場合における格子整合性の点からPZTN膜を用いることの有効性を検討した。白金系金属は、PZT系強誘電体膜を素子応用する場合に、強誘電体膜の結晶配向性を決める下地膜となるとともに、電極材料としても有用な材料である。しかし、両者の格子整合性が十分でないため、素子応用に関しては、強誘電体膜の疲労特性が問題となってくる。
図43に示す構造のサンプルを作製し、各種方法により深さ方向の元素ごとの割合を分析した。以下に、サンプルの作製方法を説明する。
電極(白金層)への酸素原子の拡散距離は、図46および図47に示す方法によって求めた。
また、AESではスパッタ時間で深さを規定しているので、スパッタレートを一定であると仮定して距離を比較することで拡散距離を求めている。具体的には、図47に示すように、酸素原子のピークの裾と白金原子のピークの裾とが重なる領域の深さの幅を「深さ1(D1)」とし、白金ピークの深さの幅を「深さ2(D2)」とすると、拡散距離は、以下の式(2)で求めることができる。D1およびD2については、わかりやすい例として図45(B)に具体的に示した。
以上の式(1)、(2)を用いて、実施例のサンプルについて、RBS+NRA分析による酸素原子の拡散距離を求めたところ、15nmであった。また、実施例のサンプルについて、AES分析による酸素原子の拡散距離を求めたところ、30nmであった。これに対し、比較例のサンプルでは、RBS+NRA分析による酸素原子の拡散距離は約70nmであり、AES分析では90nmであった。
強誘電体膜における酸素原子の割合のばらつきは、以下の式(3)によって求めたものである。以下の式において、「最大値」および「最小値」は、酸素ピークでの拡散領域を除いた部分での最大値および最小値を示す。例えば、図45(B)に示すように、酸素のピークのうち、鉛が顕著に拡散している領域および白金が拡散している領域を除いた領域A100において、ピークの最大値(Max)と最小値(Min)を求める。
以上の式(3)を用いて、実施例のサンプルについて、RBS+NRA分析による酸素原子の割合のばらつきを求めたところ、1%であった。また、実施例のサンプルについて、AES分析による酸素原子の割合のばらつきを求めたところ、3%であった。これに対し、比較例のサンプルでは、RBS+NRA分析による酸素の割合のばらつきは実施例とあまり差は見られないが(その代わり、拡散領域に存在する酸素原子数が実施例に比べて格段に多い。)、AES分析では8%のばらつきがあることが確認された。
Ir電極上にPbZr0.36Ti0.44Nb0.20O3(PZTN(36/44/20)、実施例)およびPbZr0.56Ti0.44O3(PZT(56/44)、比較例)をそれぞれ約1μm積層させた強誘電体(圧電体)膜を作製した。それぞれの圧電体膜は、スピンコートにより溶液を塗布し、乾燥および脱脂させる工程を、所望の膜厚になるまで繰り返し、750℃の高速熱処理により結晶化させることにより、作製した。
本例ではPbZr0.4Ti0.6O3強誘電体膜を作製した。
図32(A)および図32(B)は、本発明の実施形態における、単純マトリクス型の強誘電体メモリ装置300の構成を示した図である。図3(A)はその平面図、図32(B)は図32(A)のA−A線に沿った断面図である。強誘電体メモリ装置300は、図32(A)および図32(B)に示すように、基板308上に形成された所定の数配列されたワード線301〜303と、所定の数配列されたビット線304〜306とを有する。ワード線301〜303とビット線304〜306との間には、上記実施の形態において説明したPZTNからなる強誘電体膜307が挿入され、ワード線301〜303とビット線304〜306との交差領域に強誘電体キャパシタが形成される。
以下に、本発明の実施形態における、インクジェット式記録ヘッドについて詳細に説明する。
Claims (9)
- 下電極と、
前記下電極上に形成された強誘電体膜と、
前記強誘電体膜上に形成された上電極と、
を備え、
前記強誘電体膜は、Pb、ZrおよびTiを含み、かつ、ペロブスカイト型結晶構造を有し、さらに5モル%以上20モル%以下のNbを含み、
前記下電極は、白金族元素または白金族元素を主体とした複合材料よりなり、
ラザフォード後方散乱分析法(RBS)および核反応分析法(NRA)により分析した前記強誘電体膜から前記下電極への酸素原子の拡散距離は、15nm以下である、圧電素子。 - 請求項1において、
前記下電極は白金からなる、圧電素子。 - 請求項1または2において、
オージェ電子分光法(AES)により分析した前記強誘電体膜から前記下電極への酸素原子の拡散距離は、30nm以下である、圧電素子。 - 請求項1ないし3のいずれかにおいて、
ラザフォード後方散乱分析法(RBS)および核反応分析法(NRA)により分析した前記強誘電体膜における酸素原子の割合のばらつきは、1%以下である、圧電素子。 - 請求項1ないし3のいずれかにおいて、
オージェ電子分光法(AES)により分析した前記強誘電体膜における酸素原子の割合のばらつきは、3%以下である、圧電素子。 - 請求項1ないし5のいずれかにおいて、
前記強誘電体膜は、さらに0.5モル%以上5モル%以下のSiまたはGeを含む、圧電素子。 - 請求項6において、
前記強誘電体膜は、前記Siを1モル%以上含む、圧電素子。 - 請求項1ないし7のいずれかに記載の圧電素子を備えた、液体噴射ヘッド。
- 請求項8に記載の液体噴射ヘッドを備えた、液体噴射装置。
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JP2005026648A JP4811556B2 (ja) | 2004-04-23 | 2005-02-02 | 圧電素子、液体噴射ヘッドおよび液体噴射装置 |
US11/104,572 US20050236654A1 (en) | 2004-04-23 | 2005-04-13 | Ferroelectric film laminated body, ferroelectric memory, piezoelectric element, liquid jet head, and printer |
DE200560012338 DE602005012338D1 (de) | 2004-04-23 | 2005-04-14 | Ferroelektrischer Kondensator, ferroelektrischer Speicher, piezoelektrisches Element, Flüssigkeitsstrahlkopf und Drucker |
EP20050008138 EP1589566B1 (en) | 2004-04-23 | 2005-04-14 | Ferroelectric capacitor, ferroelectric memory, piezoelectric element, liquid jet head, and printer |
TW94112755A TW200536108A (en) | 2004-04-23 | 2005-04-21 | Ferroelectric film laminated body, ferroelectric memory, piezoelectric element, liquid jet head, and printer |
KR20050033051A KR100719004B1 (ko) | 2004-04-23 | 2005-04-21 | 강유전체막 적층체, 강유전체 메모리, 압전 소자, 액체분사 헤드 및 프린터 |
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