JP2001523768A - 有機薄膜の低圧蒸着 - Google Patents

有機薄膜の低圧蒸着

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JP2001523768A
JP2001523768A JP2000521253A JP2000521253A JP2001523768A JP 2001523768 A JP2001523768 A JP 2001523768A JP 2000521253 A JP2000521253 A JP 2000521253A JP 2000521253 A JP2000521253 A JP 2000521253A JP 2001523768 A JP2001523768 A JP 2001523768A
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フォレスト、スチーブン、アール
バーロウズ、ポール
バン、ブラディミール、エス
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ザ、トラスティーズ オブ プリンストン ユニバーシティ
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Abstract

(57)【要約】 基体58上に有機薄膜を形成する方法であって、その方法は、複数の有機前駆物質(14、48)を気相で与え、前記複数の有機前駆物質(14、48)を減圧下で反応させる工程を有する。そのような方法により製造された薄膜及びそのような方法を実施するのに用いられる装置も含む。本方法は、有機発光デバイスの形成及び他のディスプレイ関連技術によく適している。

Description

【発明の詳細な説明】
【0001】 (技術分野) 本発明は、光学的品質の薄膜を製造することに関し、特に非線形光学デバイス
及び有機発光デバイスで利用されるそのような薄膜の低圧製造に関する。
【0002】 (背景技術) 有機エレクトロルミネッセンスの分野は、急速に成長しつつある技術分野であ
る。ディスプレイへの潜在的な用途に刺激されて、有機発光デバイス(OLED
)は、3%を越える外部量子効率を達成し、ビデオ輝度で10,000時間の程
度の作動寿命を達成することができる。低分子とポリマーの両方をベースとする
OLEDが知られているが、ポリマーベースのデバイスは回転蒸着法により簡単
で安価に製造できる一般的利点を有する。これに対し、低分子によるデバイスは
、通常真空中での熱的蒸発により製造されており、それは通常回転蒸着よりも高
価な方法である。OLED構造及び処理方法の例は、公開されたPCT出願WO
96/19792(言及することによって本明細書に組み入れる)に与えられ
ている。
【0003】 有機蒸着(organic vapor phase deposition)(OVPD)を使用することによ
り、ディスプレイ等の多くの潜在的光学的デバイス用途を持つ低分子量の有機層
の低コストで大規模な蒸着が進歩してきた。OVPD法はホレスト(Forrest)等 の米国特許第5,554,220号明細書、S.R.ホレスト等の「有機蒸着に
より成長させた有機塩薄膜の強力な二次調波発生及び長距離構造配列」(Intense
Second Harmonic Generation and Long-Range Structural Ordering in Thin F
ilms of an Organic Salt Grown by Organic Vapor Phase Deposition)、68 App
l. Phys. Lett., 1326 (1996)、及びP.E.バローズ(Burrows)等の「有機蒸 着:大きな光学的非線形性を持つ有機薄膜の新規な成長方法」(Organic Vapor P
hase Deposition: a New Method for the Growth of Organic Thin Films with
Large Optical Non-linearities)、156 J. of Crystal Growth 91 (1995)(それ
らは言及することによって本明細書に組み入れる)に記載されている。
【0004】 OVPD法は原料物質を基体へ運ぶためにキャリヤガスを用い、この場合ガス
が凝縮して希望の薄膜を形成する。例えば、OVPD法を用いて、揮発性前駆物
質、沃化4′−ジメチルアミノ−N−メチル−4−スチルバゾリウム(DASI
)及びメチルp−トルエンスルホネート(メチルトシレート、MT)をキャリヤ
ーガスにより加熱された基体へ運ぶことにより、光学的に非線形の有機(NLO
)塩、4′−ジメチルアミノ−N−メチル−4−スチルバゾリウムトシレート(
DASI)の膜を蒸着してきた。この方法ではDASIが熱分解して4−ジメチ
ルアミノ−4−スチルバゾール(DAS)を形成し、それが次にMTと反応して
基体上にDASTを形成する。
【0005】 著しく異なった蒸気圧を持つ材料を制御して同時蒸着することができるため、
OVPDは多成分薄膜の正確な化学量論的成長を行うための唯一の方法であると
考えられている。しかし、OVPD法は大気圧で行われ、大気圧又はその近くで
成長する膜は屡々粗く、気相核生成及び拡散律速成長過程により不均一な表面形
態を有する。
【0006】 (発明の開示) 本発明は、優れた表面特性を有する有機薄膜を製造するために低圧蒸着法を用
いる。一つの態様として、本発明は、基体上に有機薄膜を形成する方法において
、複数の有機前駆物質を与え、然も前記有機前駆物質は気相になっており、前記
基体を存在させて減圧で前記複数の有機前駆物質を反応させて前記基体上に薄膜
を形成する諸工程からなる方法にある。別の態様として、本発明は、そのような
方法により製造された有機膜を包含する。更に別の態様として、本発明は、大気
の常態値以下の圧力で有機前駆物質の反応を促進して基体上に有機膜を形成する
ように設計された装置を含む。
【0007】 本発明の一つの利点は、そのような膜の各成分の量を正確精密に制御すること
ができる多成分有機薄膜を与えることである。
【0008】 本発明の別の利点は、滑らかな表面を有する均一な有機薄膜を与えることであ
る。
【0009】 本発明の更に別な利点は、有機発光材料及び光学的に非線形の有機塩の薄膜を
成長させる低圧有機蒸着法及び装置を与えることである。
【0010】 本発明の更に別な利点は、有機発光材料及び光学的非線形の有機塩の薄膜を形
成させる低圧有機分子ビーム蒸着法及び装置を与えることである。
【0011】 本発明のさらに別な利点は、大きな基体領域に亙って有機材料を均一に蒸着す
る方法及び装置を与えることである。
【0012】 (詳細な説明) 本発明は、大気の常態値以下の圧力で基体上に有機薄膜を成長させるための方
法及び装置を与える。本発明の方法は、ここでは低圧有機蒸着(LPOVPD)
として規定する。本発明のLPOVPD法は、多成分有機薄膜の蒸着を正確精密
に制御することができる。更に、本発明の薄膜は、表面粗さが小さいと言った優
れた表面性を特徴とする。
【0013】 本発明の態様によるLPOVPD反応器10を図1に模式的に示す。反応器1
0は、反応管12のような反応室及び反応室中へ伸びる配管を有する。反応管1
2は、実験装置では、例えば、10cmの直径及び約45cmの長さのような適
当な大きさを有する円筒である。反応管12は、ガラス又は石英のような適当な
材料から作られている。坩堝14のような開口容器には第一有機前駆物質材料が
入っており、反応管12の一方の端20に近い管36内に配置されている。別法
として、坩堝14は直接反応管12上に置かれているか、又はその中の棚又は管
に配置されている。坩堝14は、実質的に反応管12を取り巻く多領域加熱器/
冷却器18により加熱又は冷却される。坩堝14の温度制御により、坩堝14内
の第一有機前駆物質材料の熱分解又は蒸発を与えることになる。不活性キャリヤ
ガスの調節した流れ30を、管36を通って反応室中へ送り、それにより第一有
機前駆物質の蒸気を反応管12に沿ってその排出端22の方へ流す。不活性キャ
リヤガスは、窒素、ヘリウム、アルゴン、クリプトン、キセノン、ネオン等の不
活性ガスである。水素、アンモニア、メタン等の還元性を持つガスも多くの有機
材料に対しては不活性である。これらの還元性ガスを使用することにより、望ま
しくない過剰の反応物の燃焼を助ける付加的利点が屡々得られる。
【0014】 不活性ガスは、タンク24から、調節バルブ26を通り、配管28へ入り、少
なくとも二つの流路30及び38を通って反応管12中へ送られる。一つの流路
30は、直列に接続された圧力調節器32、流量計34、及び高速切り替えバル
ブ35を有し、そこからキャリヤガスが反応管12の端20中へ送られる。第二
流路38は、直列に接続された圧力調節器40、流量計42に、及び高速切り替
えバルブ39を有し、そこからキャリヤガスがバブラー(bubbler)46中へ流れ 、そのバブラーには第二有機前駆物質材料48が入っている。第二有機前駆物質
材料48の温度制御をし易くするため、バブラー46は容器52内の浴50内に
部分的に浸漬されている。タンク24からの不活性ガスは、第二有機前駆物質4
8を気泡として通り、配管54を通って第二有機前駆物質48の蒸気を反応管1
2中へ運ぶ。この工程中、管54は、気化した第二有機前駆物質48がバブラー
から反応室へ移動する間に再び凝縮しないように充分高い温度に維持されなけれ
ばならない。
【0015】 反応管12中へ入る前駆物質の量は、キャリヤガスの温度及び流量、及び反応
物の温度のような処理パラメータにより制御される。LPOVPD法は、前駆物
質又は反応物の蒸気圧又は化学的性質とは無関係に、圧力質量流量制御器を用い
てそれらの正確な計量を与える。本発明の方法は、このようにして希望の膜の製
造に必要な比率で非常に異なった特性を持つ材料の組合せを可能にする。
【0016】 前駆物質の流れは、高速切り替えバルブ35及び39を用いることにより、殆
ど瞬間的にオン・オフの切り替えを行うことができる。これらのバルブは前駆物
質流を反応器12又はバイパス管(図示せず)中へ送り、どの時間においても異
なった前駆物質流が反応器12中へ入り、異なった組成及び特性の膜を蒸着する
ことができる。バルブ39は、バブラー46へ入るキャリヤガスの調節も行う。
バルブ35及び39は、このようにして反応器12中へ入る反応物の流れを迅速
に変化し、成長する膜の性質及び組成を変化させ得る。従って、例えば、各文字
が異なった分子層又は組成を表すものとして、ABAB、ABCABC、ABA
BCAB、及びABCDABCD−型の膜を成長させることができる。
【0017】 真空ポンプ66及び制御スロットルバルブ68を、反応器10の排気管62の
所に取付ける。基体58上に蒸着しなかった有機蒸気の殆どは、ポンプ66より
上流に配置されたトラップ64中で凝縮する。トラップ64には、例えば液体窒
素又は中性フルオロカーボンオイルが入っている。スロットルバルブ68は反応
器10中の圧力を調節する。適当な圧力ゲージを反応器に取付け(図示せず)、
反応器中に希望の圧力を維持するように制御スロットルバルブ68に電気的フィ
ードバックを行う。
【0018】 真空ポンプ66は、反応管12中に約0.001〜100トールの圧力を与え
る。受容体層、供与体層、及び単一成分層のいかなる組合せに対しても、実際の
圧力は、前駆物質材料を蒸発するために必要な温度、前駆物質材料の凝縮を防ぐ
壁温度、及び反応領域温度勾配に関連して実験的に決定する。圧力の最適選択は
、各蒸着される有機層の要件に特有のものである。例えば、トリス−(8−ヒド
ロキシキノリン)アルミニウム(Alq3)又はN,N′−ジフェニル−N,N−
ビス(3−メチルフェニル) 1,1′−ビフェニル−4,4′ジアミン(TP
D)等の単一成分層の蒸着のための最適圧力は約0.1〜10トールである。
【0019】 本発明の薄膜を蒸着する基体は、半導体及び光学デバイスを製造する場合に一
般に使用される材料から選択されるのが典型的である。例えば、そのような材料
には、ガラス、石英、珪素、砒化ガリウム及び他のIII−V半導体、アルミニウ ム、金及び他の貴金属及び卑金属、ポリマー膜、二酸化珪素及び窒化珪素、イン
ジウム錫酸化物等が含まれる。高品質の光学的薄膜のためには、蒸着した有機膜
と結晶性相互作用を与えてエピタキシャル成長を起こす基体を用いるのが好まし
い。そのようなエピタキシャル成長を達成するためには、蒸着すべき膜と同様な
結晶構造を有する非極性有機物で基体を被覆することが屡々必要である。
【0020】 更に、有機薄膜を基体58上に蒸着する場合、基体の温度を制御することが屡
々好ましい。基体温度の独立した制御は、例えば、水、ガス、フレオングリセリ
ン、液体窒素等の物質を循環させるためのチャンネルを有する温度制御ブロック
60を基体58と接触させることにより達成する。基体は、ブロック60上又は
その近くに配置した抵抗又は輻射線加熱器を使用することにより加熱することも
できる。
【0021】 図1の反応器20は、付加的前駆物質を反応器20中へ供給するように多重バ
ブラー46Nを含ませるように拡大し得る。同様に、多重キャリヤガス流路30
Nを用いて坩堝14Nからの更に付加的前駆物質を送る。別法として、坩堝14
、14Nは、付加的前駆物質を処理するため反応管12中の棚上又は管中に垂直
方向に重ねることもできる。蒸着すべき有機膜により、一つ以上の流路30及び
38を単独又は組合せて用い、必要な前駆物質材料を与えることができる。
【0022】 本発明の方法を用いて、極めて多種の有機薄膜を蒸気前駆物質の反応により蒸
着することができる。ここで用いる「反応」とは、前駆物質反応物が明確な反応
生成物を形成する化学反応を意味するか、又は別法としてそれは前駆物質材料の
組合せ又は混合物を単に意味するか、又は前駆物質材料が供与体・受容体、又は
ゲスト・ホストの関係を形成する場合を意味する。例えば、本発明に従い、列挙
した前駆物質の反応により薄膜として次のNLO物質が形成される:
【0023】
【表1】
【0024】 OLEDを製造するのに用いられる発光材料に特に関連した別の例では、前駆
物質は、例えば、テトラチスファルバレン(tetrathisferlvalene)(TFF)及び
7,7,8,8−テトラシアノキノジメタン(TCNQ)からなる。混合工程は
、基体上に蒸着する電荷移動錯体TTF−TCNQを与える結果になる。OLE
Dに関する別の例では、4−(ジシアノメチレン)−2−メチル−6−(p−ジ
メチルアミノスチリル)−4H−ピラン(DCM)を大きな流量のキャリヤーガ
ス流中に添加し、一方、Alq3を低流量のキャリヤガス中に添加する。次にこ れらの流れを中心反応管中で混合し、それによりホストマトリックス膜中のゲス
ト分子を希望通りに希釈し、単一の発光層を形成する。Alq3ホスト中の他の ゲスト分子の例は、5,10,15,20−テトラフェニル−21H,23H−
ホルフィン(TPP)、ルブレン(Rubrene)、DCM2、クマリン等である。別 法として、効率的な広範な色の変化を達成するため、単一ホスト中に多種ドーパ
ントを添加してもよい。
【0025】 別の例として、Alq3、ビス−(8−ヒドロキシキノリン)アルミニウムオ キシフェニル〔(Alq2)′−OPh〕等の発光層(EL)の表面上に積層した
TPD、α−4,4′−ビス[N−(1−ナフチル)−N−フェニル−アミノ]
ビフェニル(α−NPD)、又はMTDATA等のホール輸送層(HTL)、又
はこれらの層のドープした組合せからなる二相発光デバイスは、連続的にHTL
及びELを希望の厚さに成長させることにより形成する。次にそれら有機層の上
に付加的層を成長させるか、又はトリメチル・インジウム、トリメチル・ガリウ
ム等のような有機金属原料を用いて金属接点(コンタクト,contact)層を成長さ せる。
【0026】 図1に関して述べた装置及び方法の外に、本発明は、図2に示すような低圧反
応器70及び方法を包含する。反応器70は、改良した超高真空室71及びバル
ブ72に接続されたターボ分子ポンプ等の真空ポンプ(図示せず)を有する。室
71中の典型的な室基底圧力は10-3〜10-11トールである。反応器70を用 いた有機層蒸着法は、有機分子ビーム蒸着(OMVD)と呼ばれている。LPO
VPD及びOMVDの両方共有機層を蒸着するのに減圧を用いているが、これら
の方法の原理的差は、後者では分子平均自由行程が室70の大きさに匹敵するか
、又はそれより大きいことである。比較として、LPOVPDの平均自由行程は
、ガス反応器の大きさよりもかなり短い。従って、OMVDはインジェクタから
基体へ高度に配向した「分子ビーム」の形成を可能にし、成長膜厚さ、純度及び
形態の正確な速度論的制御を可能にする。
【0027】 バブラー74が、第一前駆物質材料75を入れるために配備されている。バブ
ラー74は容器76中に入れられ、温度制御浴80中に浸漬されている。高純度
不活性キャリヤガス78が第一前駆物質75を気泡として通り、各蒸気を加熱さ
れた配管79を通ってインジェクタ82により真空室71中へ運ぶ。室71中に
入ると、前駆物質蒸気は分子ビーム83を形成し、それが基体85に衝突する。
基体85には、例えば、冷却剤入口81のような温度を制御するための手段が配
備されている。
【0028】 場合により、真空室71には少なくとも一つのクヌーセン又はK−セル86が
配備されており、その中には第二前駆物質材料88が入っている。K−セル86
は、真空中で蒸発物を流出させるための均一に加熱され、制御された炉である。
例えば、K−セル86はDASI又は他の前駆物質を分解するまで加熱され、得
られたDASを昇華し、それを分子ビーム89として反応器70中へ注入する。
別法として、K−セル86は、単にAlq3等の単一成分物質を昇華するだけで ある。別法として、K−セル86には、加熱によりガス流中に昇華又は蒸発され
る分子物質の濃度を希釈するのに用いられるキャリヤガス入口が取付けてある。
この希釈方法は、浴80及びクヌーセン・セル86の温度の外、バブラー74へ
のキャリヤガス78の流れを制御することにより、DCM−Alq3等のゲスト ・ホスト系の正確なドーピング量を達成するのに特に有用である。
【0029】 有機薄膜を蒸着させるため基体85に物質ビーム83及び89を衝突させ、薄
膜の厚さを石英結晶93により監視する。試料ホールダ90は回転して前駆物質
材料の均一な蒸着及び反応を確実に与える。前駆物質材料の蒸着は、更に分子ビ
ーム83及び89を遮断するのに用いられるシャッタ87により制御する。
【0030】 場合により反応器70は冷却囲い91も有し、それは、真空室71の圧力を、
再蒸発された前駆物質材料のための最小値に維持するのに役立つ。前駆物質材料
が移動して互いに汚染することがないように隔壁92を配備するのも好ましい。
【0031】 反応器70には、図1に示すLPOVPD反応器の付属品と同じもの、例えば
、高速切り替えバルブ、バイパス導管等の多くのものが配備されている。反応器
70には、多重クヌーセンセル及びバブラーを、基体85の上に複数の前駆物質
材料を蒸着するために取付けることができる。反応器70は、試料導入のための
「ロード・ロック(load-lock)」を有するのが好ましい。ロード・ロック94は ドア95及び真空ポンプ96を有し、室71の圧力を低下することなく、試料の
交換を与えることができる。
【0032】 図1の装置は、場合により、図3に説明する例によって示すように、大面積基
体上に有機層を連続的に蒸着できるように修正する。図3の装置は、導入室14
6、有機層蒸着室150及び152、接点蒸着室154、及び取出し室156の
ような複数の真空室を有する。例として、各蒸着室は図1のLPOVPD反応器
10である。基体137はコンベヤベルト148に乗せて室150、152、1
54及び156の各々を通って運ぶ。図3に示した態様では、室150、152
及び154は、夫々輻射熱源158、160及び162を有し、有機蒸気の凝縮
を防ぐ。図3には唯二つの有機層蒸着室150及び152しか示されていないが
、希望に応じて付加的室を配備する。導入室146から有機層蒸着室150及び
152へ、また接点蒸着室154から取出し室156へ送られる間に、基体13
7は空気遮断部(図示せず)を通過し、室150、152及び154の中の真空
を低下しないようにしてある。OLEDに関する例として、室150及び152
を夫々TPD及びAlq3の蒸着のために用い、室154をMg:Ag接点層を 蒸着するために用いる。
【0033】 図3の例の室150、152、及び154の各々には、図4A及び4Bに詳細
に示すように、有機前駆物質材料の蒸着のための反応物ガス分配器(RGD)1
08が含まれている。RGD108は、図1及び2の有機前駆物質導入機構の代
替物として用いられ、ガスカーテン、120、120′、120″及び120″
′を与えるのに用いられる。RGD108は、多種有機前駆物質を蒸着する場合
に、それら前駆物質が基体上に蒸着されるまで分離されているのを確実にし、そ
れにより前駆物質の反応を行わせることができる。RGD108には、加熱器1
22、第二キャリヤガス入口112及びガスマニホルド132が含まれる。加熱
器122は、有機前駆物質材料の凝縮が速過ぎるのを防ぐ。RGD108の上に
は第一キャリヤガス入口114及び分配器板110が存在する。第一キャリヤガ
ス入口114は、例えば、MT等の一般に低揮発性第一有機前駆物質を通常運ぶ
ガスを供給する。第一キャリヤガスは、例えば、ワイヤ網、ガラスフィルタ材料
、又は多孔質ステンレス鋼板である分配器板110を通って反応室へ入る。分配
器板110を通って流れるキャリヤガスのカラムは、RGD108により陰にな
っている。RGD108は、例えばDAS等の一般に低い蒸気圧の第二有機前駆
物質の平面状ガスカーテン120を与える。第二有機前駆物質を含む第二キャリ
ヤガスは、入口112から入り、ガスマニホルド132の中へ送られる。マニホ
ルド132は、環状空洞126中へ第二キャリヤガスを供給するための並んだ孔
134を有する中空管であり、その環状空洞はマニホルド132を取り巻いてい
る。第二キャリヤガスはスリット136を通ってRGD108を出、それによっ
て平面状カーテンの形態をそれに与える。
【0034】 例として、カーテン120はTPD蒸気からなり、カーテン120′はAlq 3 蒸気からなり、カーテン120″は、伝導性表面を生ずるポリピロール(polypy
role)、金属有機化合物等の蒸気からなる。もし望むならば、OLEDにより発 する光の色の制御又は調節を、Alq3層の適当なドーピングにより行うことが でき、室152中の付加的RGDデバイス108によりドーパント蒸気のカーテ
ン120″′を与える。
【0035】 図1、図2又は図3の装置は、場合により図5に示すような「ロール対ロール
」基体搬送装置を用いることにより修正する。図5に示す搬送装置は、大面積可
撓性基体上に有機薄膜を蒸着するのに適している。例えば、基体180はポリマ
ーシート又は金属箔からなり、ロール181からロール182へ送る。基体18
0への有機前駆物質の蒸着は、基体180がロール181から解かれた時に行わ
れ、従って図1の反応室へ露出されるか、又は図2及び3の分子ビーム又はカー
テンに夫々露出された時に行われる。ロール181及び182は、速度可変モー
タ等の適当な手段により駆動する。基体180がロール181からロール182
へ送られる速度は、基体180上に形成される有機膜の厚さを決定する。
【0036】 本発明を、次の諸例に関連して更に記述するが、本発明は、それら諸例に限定
されるものではない。
【0037】 例1 図1の装置を用い、インジウム錫酸化物(ITO)の透明層で予め被覆したガ
ラス及び可撓性ポリエステル基体を用いて、有機発光材料の層を成長させた。I
TOは装置のアノードを形成し、ガラス及びポリエステル基体に対し、夫々17
00Å及び1200Åの厚さを持ち、夫々10Ω及び60Ωのアノード抵抗を与
えた。ガラス基体は超音波浴中の洗剤溶液及び脱イオン水で濯ぎ、次に1,1,
1−トリクロロエタン中で沸騰させ、アセトンで濯ぎ、最後に2−プロパノール
で濯くことにより清浄にした。可撓性基体は、有機溶媒に曝すことによる損傷を
避けるため、洗剤及び2−プロパノール溶液だけで濯ぐことにより清浄にした。
【0038】 ガラス基体を反応管12中の、温度が約220℃になる位置に置いた。ITO
表面上に蒸着した第一層はTPD、ホール輸送材料であった。特に、TPD蒸気
を窒素キャリヤガスにより坩堝14から基体28へ運んだ。TPD成長条件には
、200±5℃の原料温度、100sccmの窒素キャリヤガス流量、0.50
トールの反応器圧力、及び20分の成長時間が含まれる。100sccmの窒素
流量で、装置のレイノルズ数は〜500であり、層流領域内に充分入る操作であ
ることを示していた。TPD層は100〜300Åの厚さに成長させた。
【0039】 蒸着後、TPD坩堝近くの温度を低下し、対応する窒素流を遮断した。次にA
lq3の電子輸送層を、別の窒素導管を開けて坩堝14NからAlq3蒸気を室1
2中へ運ぶことにより成長させた。Alq3成長条件には、247±8℃の原料 温度、50sccmの窒素流量、0.65トールの圧力、及び10分の成長時間
が含まれる。TPD及びAlq3の両方の蒸着中、水冷されたステンレス鋼基体 ホールダを用いて基体を15℃に維持した。TPD層は700〜1100Åの厚
さに成長させた。
【0040】 Alq3 層を蒸着した後、基体を反応器から取り出し、Mg:Ag頂部接点を
加熱蒸着により適用した。接点(コンタクト)は、1000Åの厚さの保護Ag
層を蒸着させて完成した。
【0041】 蒸着中、低い圧力を使用することにより、滑らかで均一な表面を有する有機層
を与える結果になった。例えば、TPD及びAlq3 層を原子力顕微鏡で測定し
て、夫々6〜8Å及び9〜11ÅのRMS粗さを持っていた。得られたOLED
装置は、低電圧でI∝V、高電圧でI∝V9である電流・電圧特性を示した。I 対Vのパワー法則依存性(power law dependence of I on V)が変化するターン・
オン(turn-on)電圧、VTは約6Vであった。
【0042】 例2 NLO膜を、図1に示す装置を用いて製造した。シリコーン油浴50により約
80〜100℃に温度を維持した30cm3バブラー46中にMT48を入れた 。窒素ガスを用いてMT48に気泡として通し、それによりMT蒸気をガラス管
54を通って反応管12中へ、坩堝14を約5cm越えた位置の所から導入した
。その坩堝は反応管12の床上に置かれており、DASIが入っていた。反応管
12中の圧力を約10-2トールに維持した。DAS蒸気はMT蒸気と反応し、基
体ブロック60上に支持された基体58上にDASTの固体膜を形成した。過剰
の未反応MT蒸気及び揮発性副反応生成物を排出管62から排出した。かくして
形成したDAST膜は、例えば、光学的スイッチとして有用である。
【0043】 本発明は、低圧蒸着法を用いて優れた表面特性及び正確精密な組成を有する有
機薄膜を製造する。本発明の種々の態様をここに示し記述してきたが、それらは
限定的意味を持たない。例えば、当業者はこれらの態様に或る修正を認めること
ができるであろうが、それら修正は特許請求の範囲の本質及び範囲に含まれる。
【0044】 ここに記載した本発明は、次の係属中の出願に関連して用いることができる:
「高信頼性、高効率、集積可能な有機発光デバイス及びその製法」(High Reliab
ility, High Efficiency, Integratable Organic Light Emitting Devices and
Methods of Producing Same)、シリアル番号08/774,119(1996年
12月23日出願);「多色LEDのための新規な材料」(Novel Materials for
Multicolor LED's)、シリアル番号08/850,264(1997年5月2日
出願);「有機遊離ラジカルに基づく電子輸送及び発光層」(Electron Transpor
ting and Light Emitting Layers Based on Organic Free Radicals)、シリアル
番号08/774,120(1996年12月23日出願);「多色表示デバイ
ス」(Multicolor Display Devices)、シリアル番号08/772,333(19
96年12月23日出願);「赤色光有機発光デバイス(LED)」(Red-Emitt
ing Organic Light Emitting Devices (LED's))、シリアル番号08/774,
087(1996年12月23日出願);「積層有機発光デバイスのための駆動
回路」(Driving Circuit For Stacked Organic Light Emitting Devices)、シリ
アル番号08/792,050(1997年2月3日出願);「高効率有機発光
デバイス構造体」(High Efficiency Organic Light Emitting Device Sturcture
s)、シリアル番号08/772,332(1996年12月23日出願);「真
空蒸着した非ポリマー可撓性有機発光デバイス」(Vacuum Deposited, Non-Polym
eric Flexible Organic Light Emitting Devices)、シリアル番号08/789 ,319(1997年1月23日出願);「メサピクセル構造を有するディスプ
レイ」(Displays Having Mesa Pixel Configuration)、シリアル番号08/79
4,595(1997年2月3日出願);「積層有機発光デバイス」(Stacked O
rganic Light Emitting Devices)、シリアル番号08/792,048(199
7年2月3日出願);「高コントラスト透明有機発光デバイス表示器」(High Co
ntrast Transparent Organic Light Emitting Device Display)シリアル番号0 8/821,380(1997年3月20日出願);「ホスト物質として5−ヒ
ドロキシ−キノキサリンの金属錯体を含む有機発光デバイス」(Organic Light E
mitting Devices Containing A Metal Complex of 5-Hydroxy-Quinoxaline as A
Host Materials)、シリアル番号08/838,099(1997年4月15日
出願);「大きな輝度を有する発光デバイス」(Light Emitting Devices Having
High Brightness)、シリアル番号08/844,353(1997年4月18 日出願);「有機半導体レーザ」(Organic Semiconductor Laser)、シリアル番 号60/046,061(1997年5月9日出願);「有機半導体レーザ」(O
rganic Semiconductor Laser)、シリアル番号08/859,468(1997 年5月19日出願);「飽和天然色積層有機発光デバイス」(Saturated Full Co
lor Stacked Organic Light Emitting Devices)、シリアル番号08/858, 994(1997年5月20日出願);「ホール注入促進層を有する有機発光デ
バイス」(An Organic Light Emitting Device Containing a Hole Injection En
hancement Layer)、シリアル番号08/865,491(1997年5月29日
出願);「伝導性層のプラズマ処理」(Plasma Treatment of Conductive Layers
)、シリアル番号PCT/US97/10252(1997年6月12日出願) ;「有機多色ディスプレイを製造するための薄膜パターン化」(Patterning of T
hin Films for the Fabrication of Organic Multi-color Displays)、シリアル
番号PCT/US97/10289/(1997年6月12日出願);「二重ヘ
テロ構造赤外線及び垂直空洞表面発光有機レーザ」(Double Heterostructure In
frared and Vertical Cavity Surface Emitting Organic Lasers)、シリアル番 号60/053,176(1997年7月18日出願);「オレッド含有熱安定
性不斉電荷キャリヤ材料」(Oleds Containing Thermally Stable Asymmetric Ch
arge Carrier Materials)、シリアル番号08/929,029(1997年9 月8日出願);「オレッド積層体を有する発光デバイス及び燐光体周波数逓降変
換器」(Light Emitting Device with Stack of Oleds and Phosphor Downconver
ter)、シリアル番号08/925,403(1997年9月9日出願);「有機
発光デバイス中のインジウム錫酸化物層を蒸着するための改良方法」(An Improv
ed Method for Depositing Indium Tin Oxide Layers in Organic Light Emitti
ng Devices)、シリアル番号08/928,800(1997年9月12日出願 );「オレッドの発光層中のアズラクトン関連ドーパント」(Azlactone-Related
Dopants in the Emissive Layer of an Oled)、シリアル番号08/948,1
30(1997年10月9日出願);「非金属カソードを用いた高透明性有機発
光デバイス」(A Highly Transparent Organic Light Emitting Device Employin
g A Non-Metallic Cathode)、(1997年11月3日出願)、代理人書類番号 10020/40(暫定出願)、及び「非金属カソードを用いた高透明性有機発
光デバイス」(A Highly Transparent Organic Light Emitting Device Employin
g A Non-Metallic Cathode)、(1997年11月5日出願)、代理人書類番号 10020/44、各係属中の出願は、言及することによって本明細書に組み入
れる。本発明は、係属中の米国特許出願シリアル番号08/354,674、0
8/613,207、08/632,322、及び08/693,359、及び
暫定特許出願シリアル番号60/010,013、06/024,001、及び
60/025,501(これらの各々は言及することによってその全体を本明細
書に組み入れる)の各々の主題に関連して用いることもできる。
【図面の簡単な説明】
【図1】 本発明の態様によるLPOVPD反応器の図である。
【図2】 本発明の態様によるOMVD反応器の図である。
【図3】 本発明の態様に従い、基体上に有機材料を連続的に低圧蒸着するための装置の
図である。
【図4A】 本発明の態様に従う反応物ガス分配器の平面図及び断面図である。
【図4B】 本発明の態様に従う反応物ガス分配器の平面図及び断面図である。
【図5】 本発明の態様によるロール対ロール基体搬送機構の側面図である。
【手続補正書】
【提出日】平成12年5月19日(2000.5.19)
【手続補正1】
【補正対象書類名】明細書
【補正対象項目名】特許請求の範囲
【補正方法】変更
【補正内容】
【特許請求の範囲】
───────────────────────────────────────────────────── フロントページの続き (81)指定国 EP(AT,BE,CH,CY, DE,DK,ES,FI,FR,GB,GR,IE,I T,LU,MC,NL,PT,SE),OA(BF,BJ ,CF,CG,CI,CM,GA,GN,GW,ML, MR,NE,SN,TD,TG),AP(GH,GM,K E,LS,MW,SD,SZ,UG,ZW),EA(AM ,AZ,BY,KG,KZ,MD,RU,TJ,TM) ,AL,AM,AT,AU,AZ,BA,BB,BG, BR,BY,CA,CH,CN,CU,CZ,DE,D K,EE,ES,FI,GB,GD,GE,GH,GM ,HR,HU,ID,IL,IS,JP,KE,KG, KP,KR,KZ,LC,LK,LR,LS,LT,L U,LV,MD,MG,MK,MN,MW,MX,NO ,NZ,PL,PT,RO,RU,SD,SE,SG, SI,SK,SL,TJ,TM,TR,TT,UA,U G,UZ,VN,YU,ZW (72)発明者 バン、ブラディミール、エス アメリカ合衆国 ニュージャージー、プリ ンストン、ザ グレート ロード 1061 Fターム(参考) 3K007 AB03 BA07 CA01 CA06 CB01 DA00 DB03 EB00 FA01 4K030 AA09 AA16 AA24 BA61 EA01 EA06 GA06 GA12 GA14 JA09 KA09 KA23 KA26 KA28 KA39 KA41 LA01 LA18

Claims (43)

    【特許請求の範囲】
  1. 【請求項1】 基体上に有機薄膜を形成する方法において、 複数の有機前駆物質を気相で与え、 基体を存在させて、大気の常態値以下の圧力で前記複数の有機前駆物質を反応
    させ、該基体上に薄膜を形成する、 諸工程を有する、上記方法。
  2. 【請求項2】 基体を反応室中に配置する、請求項1記載の方法。
  3. 【請求項3】 複数の有機前駆物質の一つを、反応工程前に反応室中へ輸送
    する工程を更に有する、請求項2記載の方法。
  4. 【請求項4】 輸送工程が、不活性ガスを用いて、輸送された有機前駆物質
    を反応室へ運ぶ工程を含む、請求項3記載の方法。
  5. 【請求項5】 不活性ガスを、窒素、アルゴン、ヘリウム、ネオン、クリプ
    トン及びキセノンからなる群から選択する、請求項4記載の方法。
  6. 【請求項6】 複数の有機前駆物質の少なくとも一つを、MT、DASI、
    MM、MfM、DASTh、MeOSI、DAS(Et)I、DAS(Et)O H、トルエンスルホン酸アセチル、MAf、TTF、TCNQ、DCM、Alq3 、TPP、TPD、α−NPD、MTDATA、及び(Alq2)′−OPhか らなる群から選択する、請求項1記載の方法。
  7. 【請求項7】 輸送工程前に、輸送される有機前駆物質を気化する工程を更
    に有する、請求項3記載の方法。
  8. 【請求項8】 気化工程が、輸送される有機前駆物質をバブラーへ導入する
    工程を含み;輸送工程が、前記バブラーに不活性ガスを通して前記輸送される有
    機前駆物質を反応室中に運ぶ工程を含む;請求項7記載の方法。
  9. 【請求項9】 気化工程が、輸送される有機前駆物質を開口容器中へ入れて
    、該開口容器を加熱する工程を含み;しかも、輸送工程が、前記開口容器上に不
    活性ガスを送り、前記輸送される有機前駆物質を反応室中に運ぶ工程を含む;請
    求項7記載の方法。
  10. 【請求項10】 気化工程が、 反応室中へ伸びているクヌーセン・セルの中へ、輸送される有機前駆物質を導
    入し、次いで 該クヌーセン・セルを加熱する、 諸工程を含む、請求項7記載の方法。
  11. 【請求項11】 基体を、回転試料ホールダに取付ける、請求項1記載の方
    法。
  12. 【請求項12】 大気圧の常態値以下の圧力が約10-11〜102トールの範
    囲内にある、請求項1記載の方法。
  13. 【請求項13】 請求項1に記載の方法により製造された有機膜。
  14. 【請求項14】 膜が発光材料を含む、請求項13記載の有機膜。
  15. 【請求項15】 膜が光学的非線形の材料を含む請求項13記載の有機膜。
  16. 【請求項16】 基体上に有機薄膜を形成する装置において、 反応室、 前記反応室を実質的に取り巻く加熱器、 前記反応室中へ伸びる配管、及び 前記反応室へ取付けられた真空ポンプ、 を具えた上記装置。
  17. 【請求項17】 反応室が反応管を有する、請求項16記載の装置。
  18. 【請求項18】 加熱器が多領域加熱器/冷却器である、請求項16記載の
    装置。
  19. 【請求項19】 配管が、 第一端部及び、反応室中へ伸びる第二端部を有する管、及び 前記管の第一端部に接続されたガス源、 を有する、請求項16記載の装置。
  20. 【請求項20】 管の内部に配置された開口容器であって、有機前駆物質材
    料を保持するための該開口容器を更に具えた、請求項19記載の装置。
  21. 【請求項21】 管が圧力調節器及びバルブを有する、請求項20記載の装
    置。
  22. 【請求項22】 配管が、 第一端部及び第二端部を有する第一管であって、第一管の第二端部が反応室中
    へ伸びている第一管、 第一管の第一端部に接続された、有機前駆物質材料を入れるためのバブラー、 第一端部及び第二端部を有する第二管であって、第二管の第二端部が前記バブ
    ラーに接続されている第二管、並びに 第二管の第一端部に接続されたガス源、 を有する、請求項16に記載の装置。
  23. 【請求項23】 第二管が圧力調節器及びバルブを有する、請求項22に記
    載の装置。
  24. 【請求項24】 基体と接触し、中にチャンネルを有する温度制御ブロック
    を更に具えた、請求項16記載の装置。
  25. 【請求項25】 反応室に取付けられたトラップを更に具えた、請求項16
    記載の装置。
  26. 【請求項26】 第一ロールと第二ロールとの間に基体を通すため、反応室
    内に第一ロール及び第二ロールを更に具えた、請求項16記載の装置。
  27. 【請求項27】 基体上に有機薄膜を形成するための装置において、 反応室、 前記反応室中へ伸びるクヌーセン・セル、 基体に接続され、回転可能な試料ホールダ、及び 前記反応室に取付けられた真空ポンプ、 を具えた上記装置。
  28. 【請求項28】 反応室中へ伸びる配管を更に具え、然も、該配管が、 第一端部及び第二端部を有する第一管であって、第一管の第二端部が前記反応
    室中へ伸びている第一管、 第一管の第一端部に接続された、有機前駆物質材料を入れるためのバブラー、 第一端部及び第二端部を有する第二管であって、第二管の第二端部が前記バブ
    ラーに接続されている第二管、並びに 第二管の第一端部に接続されたガス源、 を有する、請求項27記載の装置。
  29. 【請求項29】 第一管が加熱されている、請求項27記載の装置。
  30. 【請求項30】 反応室中に冷却された囲いを更に具えた、請求項27記載
    の装置。
  31. 【請求項31】 薄膜の厚さを検出するセンサを更に具えた、請求項27記
    載の装置。
  32. 【請求項32】 センサが石英結晶である、請求項31記載の装置。
  33. 【請求項33】 反応室へ接続されたロード・ロックを更に具えた、請求項
    27記載の装置。
  34. 【請求項34】 真空ポンプがターボ分子ポンプである、請求項27記載の
    装置。
  35. 【請求項35】 第一ロールと第二ロールとの間に基体を通すため、反応室
    中に第一ロール及び第二ロールを更に具えた、請求項27記載の装置。
  36. 【請求項36】 基体上に有機薄膜を形成するための装置において、 複数の真空室で、導入室及び有機層蒸着室を含めた複数の真空室、並びに 前記複数の真空室を通過するコンベアベルトで、その上に基体を有するコンベ
    アベルト、 を具えた上記装置。
  37. 【請求項37】 有機層蒸着室が反応物ガス分配器を有する、請求項36記
    載の装置。
  38. 【請求項38】 有機層蒸着室が加熱器を有する、請求項36記載の装置。
  39. 【請求項39】 接触蒸着室を更に具えた、請求項36記載の装置。
  40. 【請求項40】 基体上に有機薄膜を形成するための装置において、 反応器、 前記反応器を加熱するための手段、 前記反応室へ有機前駆物質材料の蒸気を導入するための手段、及び 前記反応室中の圧力を大気圧より低く低下するための手段、 を具えた上記装置。
  41. 【請求項41】 OLEDを製造するための方法において、 複数の有機前駆物質を気相で与え、次いで 前記複数の有機層を大気の常態値以下の圧力で反応させる、 諸工程を有する、上記方法。
  42. 【請求項42】 有機前駆物質が発光材料である、請求項41記載の方法。
  43. 【請求項43】 反応工程が発光物質を形成する結果を与える、請求項41
    記載の方法。
JP2000521253A 1997-11-17 1998-11-16 有機薄膜の低圧蒸着 Withdrawn JP2001523768A (ja)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/972,156 US6337102B1 (en) 1997-11-17 1997-11-17 Low pressure vapor phase deposition of organic thin films
US08/972,156 1997-11-17
PCT/US1998/024424 WO1999025894A1 (en) 1997-11-17 1998-11-16 Low pressure vapor phase deposition of organic thin films

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JP2009138382A Division JP4890592B2 (ja) 1997-11-17 2009-06-09 有機薄膜の低圧蒸着
JP2010050397A Division JP5371837B2 (ja) 1997-11-17 2010-03-08 有機薄膜の低圧気相蒸着

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JP2001523768A5 JP2001523768A5 (ja) 2006-01-12

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JP2000521253A Withdrawn JP2001523768A (ja) 1997-11-17 1998-11-16 有機薄膜の低圧蒸着
JP2009138382A Expired - Lifetime JP4890592B2 (ja) 1997-11-17 2009-06-09 有機薄膜の低圧蒸着
JP2010050397A Expired - Lifetime JP5371837B2 (ja) 1997-11-17 2010-03-08 有機薄膜の低圧気相蒸着
JP2013104840A Withdrawn JP2013177692A (ja) 1997-11-17 2013-05-17 有機薄膜の低圧気相蒸着
JP2016035497A Pending JP2016104913A (ja) 1997-11-17 2016-02-26 有機薄膜の低圧気相蒸着

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JP2010050397A Expired - Lifetime JP5371837B2 (ja) 1997-11-17 2010-03-08 有機薄膜の低圧気相蒸着
JP2013104840A Withdrawn JP2013177692A (ja) 1997-11-17 2013-05-17 有機薄膜の低圧気相蒸着
JP2016035497A Pending JP2016104913A (ja) 1997-11-17 2016-02-26 有機薄膜の低圧気相蒸着

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Country Link
US (7) US6337102B1 (ja)
EP (1) EP1032722B1 (ja)
JP (5) JP2001523768A (ja)
KR (2) KR100585286B1 (ja)
AU (1) AU1412499A (ja)
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