JPH06231678A - Manufacture of electron emitting film and electron emitting element - Google Patents
Manufacture of electron emitting film and electron emitting elementInfo
- Publication number
- JPH06231678A JPH06231678A JP3736293A JP3736293A JPH06231678A JP H06231678 A JPH06231678 A JP H06231678A JP 3736293 A JP3736293 A JP 3736293A JP 3736293 A JP3736293 A JP 3736293A JP H06231678 A JPH06231678 A JP H06231678A
- Authority
- JP
- Japan
- Prior art keywords
- electron
- temperature
- film
- fine particle
- electron emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/316—Cold cathodes having an electric field parallel to the surface thereof, e.g. thin film cathodes
- H01J2201/3165—Surface conduction emission type cathodes
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- Cold Cathode And The Manufacture (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、電子線発生装置や画像
形成装置等の電子源として用いられる電子放出膜及び電
子放出素子の作製方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electron emitting film and an electron emitting element used as an electron source for an electron beam generator, an image forming apparatus and the like.
【0002】[0002]
【従来の技術】従来、簡単な構造で電子の放出が得られ
る素子として、例えば、エム アイエリンソン(M.
I.Elinson)等によって発表された冷陰極素子
が知られている[ラジオ・エンジニアリング・エレクト
ロン・フィジックス(Radio Eng.Elect
ron Phys.)第10巻,1290〜1296
頁、1965年]。これは、基板上に形成された小面積
の薄膜に、膜内に平行に電流を流すことにより、電子放
出が生ずる現象を利用するもので、一般には表面伝導形
放出素子と呼ばれている。この表面伝導形放出素子とし
ては、前記エリンソン等により開発されたSnO2 (S
b)薄膜を用いたもの、Au薄膜によるもの[ジー・デ
ィトマー:“スイン ソリド フィルムス”(G.Di
ttmer:“Thin Solid Films”)
第9巻、317頁、1972年]、ITO薄膜によるも
の[エム ハートウェル アンド シージーフォンスタ
ッド“アイイーイーイートランス”イーディーコンファ
レンス(M.Hartwelland C.G.Fon
stad:“IEEE Trans.ED Con
f.”)519頁、1975年]等が報告されている。2. Description of the Related Art Conventionally, as a device which can emit electrons with a simple structure, for example, MI Elinson (M.
I. A cold cathode device announced by Elinson et al. Is known [Radio Engineering Electron Physics (Radio Eng.
ron Phys. ) Volume 10, 1290-1296
P. 1965]. This utilizes a phenomenon in which an electron is emitted by flowing a current in parallel to a thin film having a small area formed on a substrate, and is generally called a surface conduction electron-emitting device. As the surface conduction electron-emitting device, the SnO 2 (S
b) Using thin film, using Au thin film [Gee Ditmer: "Sin Solid Films" (G. Di
ttmer: "Thin Solid Films")
Volume 9, p. 317, 1972], by ITO thin film [M Hartwell and CG Fon, M. Hartwellland CG Fon]
stad: "IEEE Trans.ED Con
f. ") Page 519, 1975], etc. are reported.
【0003】これらの表面伝導形放出素子の典型的な素
子構成を図24に示す。同図において2及び3は電気的
接続を得るための電極、5は電子放出材料で形成される
薄膜、1は基板、4は電子放出部を示す。従来、これら
の表面伝導形放出素子においては、電子放出を行なう前
に予めフォーミングと呼ばれる通電加熱処理によって電
子放出部を形成する。即ち、前記電極2と電極3の間に
電圧を印加する事により、薄膜5に通電し、これにより
発生するジュール熱で薄膜5を局所的に破壊、変形もし
くは変質せしめ、電気的に高抵抗な状態にした電子放出
部4を形成することにより電子放出機能を得ている。
尚、電気的に高抵抗な状態とは、薄膜5の一部に、0.
5μm〜5μmの長さの亀裂を有し、かつ亀裂内がいわ
ゆる島構造を有する不連続状態膜を言う。島構造とは一
般に数十オングストロームから数ミクロンメーター径の
微粒子が基板1にあり、各微粒子は空間的に不連続で電
気的には連続な膜をいう。従来、表面伝導形放出素子は
上述の高抵抗不連続膜に電極2,3により電圧を印加
し、素子表面に電流を流すことにより、上述微粒子より
電子を放出せしめるものである。FIG. 24 shows a typical device configuration of these surface conduction electron-emitting devices. In the figure, 2 and 3 are electrodes for obtaining electrical connection, 5 is a thin film formed of an electron emitting material, 1 is a substrate, and 4 is an electron emitting portion. Conventionally, in these surface conduction electron-emitting devices, an electron-emitting portion is formed in advance by an energization heating process called forming before the electron emission. That is, by applying a voltage between the electrodes 2 and 3, the thin film 5 is energized, and the thin film 5 is locally destroyed, deformed or altered by the Joule heat generated thereby, and the electrical resistance is high. An electron emission function is obtained by forming the electron emission portion 4 in the state.
Incidentally, the electrically high resistance state means that a part of the thin film 5 has a resistance of 0.
It refers to a discontinuous state film having a crack with a length of 5 μm to 5 μm and having a so-called island structure inside the crack. The island structure generally refers to a film in which fine particles having a diameter of several tens of angstroms to several microns are present on the substrate 1, and each fine particle is spatially discontinuous and electrically continuous. Conventionally, a surface conduction electron-emitting device is one in which electrons are emitted from the above-mentioned fine particles by applying a voltage to the above-mentioned high resistance discontinuous film by means of electrodes 2 and 3 and causing a current to flow on the device surface.
【0004】また、本発明者らは、特開平1−2005
32号公報及び特開平2−56822号公報において、
電極間に電子を放出せしめる微粒子を分散配置した表面
伝導形放出素子を技術開示した。この電子放出素子は、
(1)高い電子放出効率が得られる。(2)構造が簡単
であるため、製造が容易である。(3)同一基板上に多
数の素子を配列形成できる。等の利点を有する素子であ
る。これらの表面伝導形放出素子の典型的な素子構成を
図25に示す。図25において、2及び3は電気的接続
を得るための電極、6は電子放出せしめる微粒子が分散
配置した電子放出部、1は基板である。The inventors of the present invention have also disclosed in Japanese Patent Laid-Open No. 2005-2005.
No. 32 and JP-A-2-56822,
A technology of a surface conduction type emission device in which fine particles for emitting electrons are dispersedly arranged between electrodes has been disclosed. This electron-emitting device is
(1) High electron emission efficiency can be obtained. (2) Since the structure is simple, manufacturing is easy. (3) A large number of elements can be arrayed and formed on the same substrate. It is an element having advantages such as. FIG. 25 shows a typical device configuration of these surface conduction electron-emitting devices. In FIG. 25, 2 and 3 are electrodes for obtaining electrical connection, 6 is an electron emitting portion in which fine particles for emitting electrons are dispersed, and 1 is a substrate.
【0005】以上述べた従来の表面伝導形放出素子の電
気特性(電流−電圧特性)について、図26を用いて説
明するならば、従来の電子放出素子は、放出電子は一定
の素子電圧(素子に印加される電圧)Veから急激に増
加し、素子電圧Vdで、例えば上記画像形成装置におい
て画像形成するのに充分な電子線を放出し得る。また、
素子電流(素子に流れる電流)Ifは素子電圧の上昇と
ともに増加し、素子電圧Ve付近から増加割合が高くな
る。一般にこれら従来の素子は電子放出に無関係な電
流、即ち、同図に示す大きな無効電流が流れるものであ
るが、かかる無効電流の素子電流Ifに対する割合は、
50パーセント程度にまで及ぶ場合がある。このような
無効電流の増加は、電子放出素子の駆動時の消費電力の
増加、電子放出素子の発熱による電子放出特性(電子放
出効率、放出電子の安定性等)を低下せしめるものであ
る。また、上記無効電流の増加は、以下の様な問題点を
も生み出す。すなわち、無効電流の大きな電子放出素子
を画像形成装置等の電子源に用いた場合、 (1).無効電流が配線電流に流れ、電圧降下が生じる
ために電子放出量が電子放出素子によって異なる。 (2).無効電流が形成する画像の種類(即ち、入力さ
れる情報信号の違い)によって変化するため、配線電極
での電圧降下が変化し、素子から放出される電子量が変
動する。The electrical characteristics (current-voltage characteristics) of the conventional surface conduction electron-emitting device described above will be described with reference to FIG. 26. In the conventional electron-emitting device, emitted electrons have a constant device voltage (device). The applied voltage V.sub.e can be rapidly increased, and at the element voltage Vd, for example, an electron beam sufficient for forming an image in the image forming apparatus can be emitted. Also,
The element current (current flowing in the element) If increases as the element voltage rises, and the rate of increase increases from around the element voltage Ve. Generally, in these conventional devices, a current irrelevant to electron emission, that is, a large reactive current shown in the figure flows, but the ratio of the reactive current to the device current If is:
It may reach up to 50%. Such an increase in the reactive current causes an increase in power consumption when the electron-emitting device is driven and a deterioration in electron emission characteristics (electron emission efficiency, stability of emitted electrons, etc.) due to heat generation of the electron-emitting device. In addition, the increase of the reactive current also causes the following problems. That is, when an electron-emitting device having a large reactive current is used for an electron source such as an image forming apparatus, (1). Since the reactive current flows in the wiring current and a voltage drop occurs, the amount of electron emission varies depending on the electron-emitting device. (2). Since the reactive current changes depending on the type of image formed (that is, the difference in the input information signal), the voltage drop at the wiring electrode changes, and the amount of electrons emitted from the element also changes.
【0006】以上の問題点は結局、形成画像のコントラ
スト及び鮮明性の低下、特に、形成画像が蛍光画像であ
る場合には、蛍光画像の輝度のバラツキ、輝度変化をも
たらし、画像形成装置の高精細化、大画面化が困難とな
り、また、消費電力の増大にもつながる。The above problems result in deterioration of the contrast and sharpness of the formed image, and particularly when the formed image is a fluorescent image, the brightness of the fluorescent image varies and the brightness changes, resulting in high image forming apparatus. It becomes difficult to make the screen finer and the screen larger, and it also leads to an increase in power consumption.
【0007】そこで更に本発明者らは上記問題点に鑑
み、特願平4−268714号において、電子放出効
率,放出電子の安定性等の電子放出特性に優れ、消費電
力,無効電流が極めて小さく、画像形成装置の電子源に
用いた場合に形成画像のコントラスト及び鮮明性に優れ
た新規な電子放出素子を技術開示した。In view of the above problems, the inventors of the present invention have proposed in Japanese Patent Application No. 4-268714 excellent electron emission characteristics such as electron emission efficiency and stability of emitted electrons, and have extremely low power consumption and reactive current. The present invention has disclosed a novel electron-emitting device having excellent contrast and sharpness of a formed image when used as an electron source of an image forming apparatus.
【0008】以下に、この電子放出素子について詳述す
る。まず、この電子放出素子の主たる特徴部分につい
て、図27(平面図)、図28(図27のA−A’断面
図)及び図29(図28のB−B’断面図)を用いて説
明する。これらの図において、1は絶縁性基体、2及び
3は電極、5は電子放出領域、4は電子放出領域5より
も低抵抗の微粒子膜、6は電子放出領域5に分散配置さ
れた微粒子を示す。かかる電子放出素子は、第1に、微
粒子6が分散配置された電子放出領域5と該領域5内部
に電圧を印加するための電極2及び3を必須の構成要件
とする。即ち、上記電子放出素子は電極2,3間に印加
される電圧により電子放出領域5に電子(電流)が流
れ、該電子が該領域内部の微粒子6により形成されたギ
ャップ(微粒子同志の間隙)により該領域外へ放出され
るという機構を有する素子である。尚、上記低抵抗の微
粒子膜4は、電子放出領域5と電極2及び3との電気的
接触をより一層向上させる目的で、配置されている。ま
た、電子放出領域5及び微粒子膜4を構成する微粒子は
いずれも導電性材料が用いられる。The electron-emitting device will be described in detail below. First, the main characteristic portion of this electron-emitting device will be described with reference to FIG. 27 (plan view), FIG. 28 (AA ′ cross-sectional view of FIG. 27) and FIG. 29 (BB ′ cross-sectional view of FIG. 28). To do. In these figures, 1 is an insulating substrate, 2 and 3 are electrodes, 5 is an electron emission region, 4 is a fine particle film having a resistance lower than that of the electron emission region 5, and 6 is fine particles dispersed in the electron emission region 5. Show. In such an electron-emitting device, first, the electron-emitting region 5 in which the fine particles 6 are dispersed and the electrodes 2 and 3 for applying a voltage to the inside of the region 5 are essential constituent elements. That is, in the electron-emitting device, electrons (current) flow in the electron-emitting region 5 by the voltage applied between the electrodes 2 and 3, and the electrons are formed by the fine particles 6 inside the region (gap between fine particles). It is an element having a mechanism of being released to the outside of the region by. The low resistance fine particle film 4 is arranged for the purpose of further improving the electrical contact between the electron emission region 5 and the electrodes 2 and 3. In addition, a conductive material is used for both the fine particles forming the electron emission region 5 and the fine particle film 4.
【0009】また、上記の電子放出素子は上記必須の構
成要件に加え、以下に述べる2つの態様を有するもので
ある。Further, the above electron-emitting device has the following two modes in addition to the above essential constituent elements.
【0010】まず、第1の態様では、上記電子放出領域
5内における、微粒子6の面積占有率が20%〜75%
の範囲内にある。ここで、図30及び図31は上述の電
子放出素子のSEM(走査型電子顕微鏡)写真の模写図
であり、図30は、図28のA−A’領域を上から観察
した場合の平面図、図31は、図29のB−B’領域を
上から観察した場合の平面図、更に、図31の点線領域
は、電子放出領域5をより高倍率でSEMにて観察した
場合の拡大図に相当する。尚、前記微粒子の面積占有率
とは、次の様に測定される値を意味する。まず、図31
の点線領域で示されるように、素子の電子放出領域5内
部のSEM像(STM(走査型トンネル顕微鏡)像でも
良い)を、微粒子数が10個〜1000個観察し得る倍
率にて採り、かかるSEM像から、全面積に対し全微粒
子の面積が占める割合を測定する。この測定を電子放出
領域5の全領域にわたり行い、得られた測定値の平均値
を算出して、これを上記微粒子の面積占有率としてい
る。First, in the first mode, the area occupancy of the fine particles 6 in the electron emission region 5 is 20% to 75%.
Is within the range of. 30 and 31 are SEM (scanning electron microscope) photographs of the electron-emitting device described above, and FIG. 30 is a plan view of the area AA ′ in FIG. 28 observed from above. 31 is a plan view of the BB ′ region of FIG. 29 observed from above, and the dotted line region of FIG. 31 is an enlarged view of the electron emission region 5 observed by SEM at a higher magnification. Equivalent to. The area occupancy of the fine particles means a value measured as follows. First, FIG.
As shown by the dotted line region, a SEM image (or STM (scanning tunneling microscope) image may be used) of the inside of the electron emission region 5 of the device is taken at a magnification such that 10 to 1000 fine particles can be observed. From the SEM image, the ratio of the area of all the fine particles to the total area is measured. This measurement is performed over the entire area of the electron emission area 5, the average value of the obtained measurement values is calculated, and this is taken as the area occupancy of the fine particles.
【0011】上述の電子放出素子において、微粒子の面
積占有率と上述した無効電流との関係、更には、電子放
出特性との関係は次の様に考えられる。即ち、前記微粒
子の面積占有率が大きすぎると、電子放出領域全体に占
める前記ギャップ(微粒子同志の間隙)の割合が小さく
なりすぎるため、電子放出領域は連続膜としての性状を
呈することとなり、連続膜を流れる電子量が大きくなる
と共に、放出される電子量が小さくなり、結局、素子の
無効電流が大きくなってしまう。一方、前記微粒子の占
有面積が小さすぎると、上記ギャップの割合が大きくな
りすぎるため、電子放出のための印加電圧が大きくなる
ので、一度放出された電子が電極に引き戻されてしまう
現象が生じるため、この場合もまた素子の無効電流が大
きくなってしまい、また、放出される電子量も少なくな
ってしまうと考えられる。In the electron-emitting device described above, the relationship between the area occupancy ratio of the particles and the above-mentioned reactive current, and further the relationship with the electron-emitting characteristics are considered as follows. That is, when the area occupancy of the fine particles is too large, the ratio of the gap (gap between the fine particles) to the entire electron emission region becomes too small, and therefore the electron emission region exhibits a property as a continuous film. As the amount of electrons flowing through the film increases, the amount of emitted electrons also decreases, which eventually increases the reactive current of the device. On the other hand, if the area occupied by the fine particles is too small, the ratio of the gap becomes too large, so that the applied voltage for electron emission becomes large, so that the phenomenon that once emitted electrons are pulled back to the electrode occurs. Also in this case, it is considered that the reactive current of the device also becomes large and the amount of emitted electrons also becomes small.
【0012】更に、かかる第1の態様において、電子放
出領域に分散配置される微粒子の平均粒径は、5Å〜3
00Åの範囲に設定されていることが好ましく、特に好
ましくは、5Å〜80Åの範囲に設定されていることが
望ましい。即ち、上記範囲に設定されていることは、極
端に大きな粒径の微粒子自体に流れる無効電流をも防ぐ
ことができ、素子全体としての無効電流をより一層低減
することができる上、電子放出効率及び放出電子の安定
性(特に、放出電子の揺らぎ)をも一層低減できる。Further, in the first aspect, the average particle size of the fine particles dispersedly arranged in the electron emission region is 5Å to 3
It is preferably set in the range of 00Å, particularly preferably in the range of 5Å to 80Å. That is, by setting it in the above range, it is possible to prevent the reactive current flowing through the particles themselves having an extremely large particle diameter, further reduce the reactive current of the entire device, and further improve the electron emission efficiency. Also, the stability of the emitted electrons (in particular, the fluctuation of the emitted electrons) can be further reduced.
【0013】次に、第2の態様では、電子放出領域5内
における微粒子6の微粒子間隔が5Å〜100Åの範囲
内にある。尚、前記微粒子間隔とは、図29のSで示さ
れる様に微粒子同志の間隙幅を意味し、次の様に測定さ
れる値である。まず、図31の点線領域で示されるよう
に、素子の電子放出領域5内部のSEM像(STM(走
査型トンネル顕微鏡)像でも良い)を、微粒子数が10
個〜1000個観察し得る倍率にて採り、かかるSEM
像から、全ての微粒子間隙を測定する。この測定を電子
放出領域5の全領域にわたり行い、得られた測定値の平
均値を算出して、これを上記微粒子間隔としている。Next, in the second mode, the fine particle spacing of the fine particles 6 in the electron emission region 5 is in the range of 5Å to 100Å. The fine particle spacing means the gap width between the fine particles as shown by S in FIG. 29, and is a value measured as follows. First, as shown by the dotted line area in FIG. 31, an SEM image (or STM (scanning tunneling microscope) image may be used) of the inside of the electron emission region 5 of the device shows that the number of fine particles is 10
This SEM is taken at a magnification that allows observation of 1 to 1000 pieces
From the image, measure all particle spacing. This measurement is performed over the entire area of the electron emission region 5, the average value of the obtained measurement values is calculated, and this is set as the above-mentioned fine particle interval.
【0014】上述の電子放出素子において、微粒子間隔
と上述した無効電流との関係、及び、電子放出特性との
関係は、第1の態様同様に次の様に考えられる。即ち、
前記微粒子の間隔が小さすぎると、電子放出領域全体に
占める前記ギャップ(微粒子同志の間隙)の割合が小さ
くなりすぎるため、電子放出領域は連続膜としての性状
を呈する。一方、前記微粒子の間隔が大きすぎると、上
記ギャップの割合が大きくなりすぎるため、電子放出の
ための印加電圧が大きくなるので、一度放出された電子
が電極に引き戻されてしまう現象が生じる。In the above-mentioned electron-emitting device, the relationship between the particle spacing and the above-mentioned reactive current and the relationship with the electron-emitting characteristic are considered as follows, as in the first aspect. That is,
If the spacing between the fine particles is too small, the ratio of the gap (the gap between the fine particles) to the entire electron emitting region becomes too small, so that the electron emitting region has a property as a continuous film. On the other hand, if the distance between the fine particles is too large, the ratio of the gap becomes too large, and the applied voltage for electron emission increases, so that the once-emitted electron is pulled back to the electrode.
【0015】更に、かかる第2の態様においても、前記
第1の態様と同様の理由で、該電子放出領域に分散配置
される微粒子の平均粒径は、5Å〜300Åの範囲に設
定されていることが好ましく、特に好ましくは、5Å〜
80Åの範囲に設定されていることが望ましい。Further, also in the second aspect, for the same reason as in the first aspect, the average particle size of the fine particles dispersedly arranged in the electron emission region is set in the range of 5Å to 300Å. It is preferable, and particularly preferable that the range from 5Å to
It is desirable to set it in the range of 80Å.
【0016】また、上記特願平4−268714号にお
いては、上述したような電子放出領域における微粒子の
面積占有率或いは微粒子間隔、及び微粒子粒径を得るた
めに、有機金属化合物の熱処理を行っている。Further, in the above-mentioned Japanese Patent Application No. 4-268714, the heat treatment of the organometallic compound is carried out in order to obtain the area occupancy rate of fine particles in the electron emission region or the fine particle spacing and the fine particle diameter. There is.
【0017】[0017]
【発明が解決しようとする課題】以上述べたように、電
子放出部領域に電子放出材となる微粒子からなる膜が形
成されている表面伝導形放出素子においては、電子放出
領域における微粒子の面積占有率或いは微粒子間隔、及
び微粒子粒径を制御することにより、電子放出効率や電
子放出特性を向上できる訳であるが、従来の有機金属化
合物の熱処理方法においては、必ずしも安定した制御が
行なわれている訳ではない。As described above, in the surface conduction electron-emitting device in which the film made of the fine particles serving as the electron-emitting material is formed in the electron-emitting region, the area occupancy of the fine particles in the electron-emitting region is occupied. It is possible to improve the electron emission efficiency and the electron emission characteristics by controlling the rate, the interval between the fine particles, and the particle size of the fine particles. However, stable control is always performed in the conventional heat treatment method of the organometallic compound. It doesn't mean that.
【0018】従って本発明の目的は、微粒子から成る電
子放出膜の均一性(膜厚,微粒子径等),再現性をより
一層向上すると共に、その膜抵抗の制御を可能とする電
子放出膜の作製方法、更には、電子線発生装置や画像形
成装置等の電子源として用いられ、その電子放出効率や
電子放出特性に優れた電子放出素子を安定して再現性良
く作製する方法を提供することにある。Therefore, an object of the present invention is to improve the uniformity (film thickness, particle diameter, etc.) and reproducibility of an electron emission film made of fine particles, and to control the film resistance of the electron emission film. To provide a method for producing an electron-emitting device, which is used as an electron source for an electron beam generator, an image forming apparatus, and the like, and which has excellent electron emission efficiency and electron emission characteristics, with good reproducibility. It is in.
【0019】[0019]
【課題を解決するための手段及び作用】上記目的を達成
するために成された本発明は、基体上に形成した有機金
属膜を熱処理することにより電子放出膜を作製する方法
において、上記熱処理時に上記有機金属の分解温度以上
の温度Tbまで昇温する際、有機金属の融点±10℃の
温度以上且つ有機金属の分解温度未満の温度Taで一定
期間保持することを特徴とする電子放出膜の作製方法で
あり、更には、基体上の電極間に形成した有機金属膜を
熱処理することにより電子放出素子を作製する方法にお
いて、電子放出膜を作製する際に、上記の電子放出膜の
作製方法を用いることを特徴とする電子放出素子の作製
方法である。The present invention, which has been made to achieve the above object, provides a method for producing an electron emission film by heat-treating an organometallic film formed on a substrate. When the temperature is raised to a temperature Tb which is equal to or higher than the decomposition temperature of the organic metal, a temperature Ta which is equal to or higher than the melting point of the organic metal ± 10 ° C. and lower than the decomposition temperature of the organic metal is maintained for a certain period of time. A method for producing an electron-emitting device by heat-treating an organometallic film formed between electrodes on a substrate, which is the above-mentioned method for producing an electron-emitting film. Is used to fabricate an electron-emitting device.
【0020】先述した様な微粒子から成る電子放出膜の
作製方法としては、差動排気による真空蒸着法,有機金
属膜の熱分解法等が挙げられるが、均一で粒径の揃った
微粒子膜を得るには後者の方が好ましく、本発明におい
ても後者の方法を用いている。As a method for producing an electron emission film made of fine particles as described above, there are a vacuum vapor deposition method by differential evacuation, a thermal decomposition method of an organic metal film and the like, but a fine particle film having a uniform and uniform particle size is used. The latter method is preferable for obtaining the same, and the latter method is also used in the present invention.
【0021】本発明に係る有機金属膜は、例えば有機溶
剤,有機バインダー等に有機金属錯体を溶解,分散し、
溶液中の有機金属錯体の含有量を制御した後、スピナー
法,ディッピング法,スプレー法等により基体上に形成
することができる。尚、基体上への有機金属錯体の形成
量を制御できれば、上記溶剤等を用いることなく直接、
基体上に形成してもかまわない。The organometallic film according to the present invention is prepared by dissolving and dispersing an organometallic complex in, for example, an organic solvent or an organic binder,
After controlling the content of the organometallic complex in the solution, it can be formed on the substrate by a spinner method, a dipping method, a spray method or the like. In addition, if the amount of the organometallic complex formed on the substrate can be controlled, the solvent can be directly used without using the solvent.
It may be formed on the substrate.
【0022】上記有機金属錯体の形成量を制御すること
により、後述する熱処理において作製される電子放出膜
中の微粒子の粒径をある程度制御することができる。By controlling the amount of the above-mentioned organometallic complex formed, the particle size of the fine particles in the electron emission film produced in the heat treatment described later can be controlled to some extent.
【0023】この様にして形成した有機金属膜を熱処理
することにより電子放出材となる微粒子から成る電子放
出膜(微粒子膜)を作製する訳であるが、本発明者らの
研究によれば、熱処理における昇温プロセスが、それに
よって形成される微粒子膜の形状(膜厚,微粒子径等)
に非常に重要であることが判明した。The organic metal film thus formed is heat-treated to produce an electron emission film (fine particle film) made of fine particles to be an electron emission material. According to the research conducted by the present inventors, Shape of fine particle film (thickness, fine particle diameter, etc.)
Turned out to be very important to.
【0024】即ち、本発明においては、上記熱処理時に
有機金属の分解温度以上の温度Tbまで昇温する際、有
機金属の融点±10℃の温度以上且つ有機金属の分解温
度未満の温度Taで一定期間保持する。これにより、基
体上に形成された有機金属が一様に基体上に展開し均一
になり、次いで該有機金属の分解温度以上の温度Tbで
熱処理すると、有機金属が微粒子に形成され、基体上に
二次元的に一層の状態で形成される。上記温度Taでの
温度保持期間は有機金属材料及び基体上への形成量等に
より、その必要最低限の時間は若干異なるが、1分以上
であることが好ましく、1分未満であると上記材料及び
形成量によっては、十分に基体上に均一に展開できなく
なり、その後に形成される微粒子膜の膜厚(層数や微粒
子径等)が不均一になる。That is, in the present invention, when the temperature is raised to the temperature Tb which is higher than the decomposition temperature of the organic metal during the heat treatment, it is constant at the temperature Ta which is higher than the melting point of the organic metal ± 10 ° C. and lower than the decomposition temperature of the organic metal. Hold for a period. As a result, the organic metal formed on the substrate is uniformly spread on the substrate and becomes uniform. Then, when heat treatment is performed at a temperature Tb that is equal to or higher than the decomposition temperature of the organic metal, the organic metal is formed into fine particles and is formed on the substrate. It is formed two-dimensionally in a single layer. The minimum required time for the temperature holding period at the temperature Ta is slightly different depending on the amount of the organic metal material and the amount formed on the substrate, but it is preferably 1 minute or more, and if it is less than 1 minute, Also, depending on the amount of formation, it may not be possible to sufficiently spread it evenly on the substrate, and the film thickness (number of layers, particle size, etc.) of the fine particle film formed thereafter may become uneven.
【0025】また、本発明者らの研究によれば、前記温
度Tbが有機金属の分解温度よりも20℃〜100℃高
い温度であることが微粒子間隙の均一化や微粒子膜厚の
より一層の均一化にとって重要であることが判明した。Further, according to the research conducted by the present inventors, the fact that the temperature Tb is 20 ° C. to 100 ° C. higher than the decomposition temperature of the organic metal further improves the uniformity of fine particle gaps and the fine particle thickness. It was found to be important for homogenization.
【0026】上記温度Tbが上記範囲未満であると効率
的なフォーミングが行なえない、上記範囲を超えると微
粒子粒経が不均一となり、いずれの場合も極めて均一な
形状を有する微粒子膜の形成を疎外する。If the temperature Tb is less than the above range, efficient forming cannot be performed, and if the temperature Tb exceeds the above range, the particle diameter of the fine particles becomes nonuniform, and in any case, formation of a fine particle film having an extremely uniform shape is excluded. To do.
【0027】更に、均一な形状を有する微粒子膜の形成
には、上記温度Tbに1分以上一定に保持することが好
ましく、また更には、上記温度Taまでの昇温速度が1
℃/分以上であること、また、温度Taまでの昇温速度
が、温度Taから温度Tbまでの昇温速度以上であるこ
とが好ましい。Further, in order to form a fine particle film having a uniform shape, it is preferable to maintain the temperature Tb at a constant level for 1 minute or more, and furthermore, the rate of temperature increase up to the temperature Ta is 1.
It is preferable that the temperature is not less than ° C / min, and that the rate of temperature rise up to the temperature Ta is not less than the rate of temperature rise from the temperature Ta to the temperature Tb.
【0028】上記の様な熱処理工程により形成される電
子放出膜は、導電性微粒子から形成された膜、あるい
は、これら導電性微粒子が分散されたカーボン薄膜等が
挙げられる。中でも特に、その材料の具体例を挙げるな
らばPd、Nb、Mo、Rh、Hf、Ta、W、Re、
Ir、Pt、Ti、Au、Ag、Cu、Cr、Al、C
o、Ni、Fe、Pb、Cs、Ba等の金属、LaB
6 、CeB6 、HfB4 、GdB4 、等の硼化物、Ti
C、ZrC、HfC、TaC、SiC、WC等の炭化
物、TiN、ZrN、HfN等の窒化物、PdO、Ir
2 O3 、SnO2 、Sb2 O3 等の金属酸化物、Si、
Ge等の半導体、カーボン、AgMg、NiCr、Pb
Sn等である。また、電子放出膜のシート抵抗は1×1
03 Ω/□から1×1010Ω/□の範囲内にあることが
好ましい。Examples of the electron emission film formed by the heat treatment process as described above include a film formed of conductive fine particles, a carbon thin film in which these conductive fine particles are dispersed, and the like. Among them, Pd, Nb, Mo, Rh, Hf, Ta, W, Re, and
Ir, Pt, Ti, Au, Ag, Cu, Cr, Al, C
Metals such as o, Ni, Fe, Pb, Cs and Ba, LaB
Boride such as 6 , CeB 6 , HfB 4 , GdB 4 , etc., Ti
Carbides such as C, ZrC, HfC, TaC, SiC and WC, nitrides such as TiN, ZrN and HfN, PdO and Ir
2 O 3 , SnO 2 , Sb 2 O 3 and other metal oxides, Si,
Semiconductors such as Ge, carbon, AgMg, NiCr, Pb
Sn and the like. The sheet resistance of the electron emission film is 1 × 1.
It is preferably in the range of 0 3 Ω / □ to 1 × 10 10 Ω / □.
【0029】本発明に係る電子放出素子の構造は基本的
には図27〜図29に示したものと同一であるため、こ
れらの図を用いて作製方法の具体例を説明する。Since the structure of the electron-emitting device according to the present invention is basically the same as that shown in FIGS. 27 to 29, a specific example of the manufacturing method will be described with reference to these drawings.
【0030】まず、石英基板等からなる絶縁性基体1上
に電極2,3を形成する。この時の電極間隔(図27中
のG)は0.2μm〜5μmの範囲であるのが好まし
い。First, the electrodes 2 and 3 are formed on the insulating substrate 1 made of a quartz substrate or the like. At this time, the electrode interval (G in FIG. 27) is preferably in the range of 0.2 μm to 5 μm.
【0031】絶縁性基体1としては、石英基板の他にも
青板,白板等のガラス基板、Al2O3 ,SiO2 ,S
iN等の絶縁性膜、SiOx ,SnOx 等の真空成膜等
による絶縁性膜等、絶縁性を有するものであれば、どの
様なものであっても構わない。As the insulating substrate 1, besides a quartz substrate, a glass substrate such as a blue plate and a white plate, Al 2 O 3 , SiO 2 , S, etc.
Any material may be used as long as it has an insulating property, such as an insulating film made of iN or the like, an insulating film made of SiO x or SnO x by vacuum film formation, or the like.
【0032】次に先述した様な有機金属錯体を溶解した
溶媒を電極間に塗布し、本発明の電子放出膜の作製方法
に係る熱処理をすることにより電子放出材料から成る微
粒子膜4を形成する。Next, a solvent in which the above-mentioned organometallic complex is dissolved is applied between the electrodes, and the heat treatment according to the method for producing the electron emission film of the present invention is performed to form the fine particle film 4 made of the electron emission material. .
【0033】この様にして形成された微粒子膜4は、基
体1上に二次元的に一層の状態で形成される。また、上
記のごとく形成された微粒子膜は、走査型電子顕微鏡等
の分析法により容易に同定できる。さらに、微粒子膜を
構成する微粒子の粒径は、熱処理前の有機金属錯体の基
体上への形成量によって制御することができる。さらに
上記微粒子の粒径のばらつきは、先述した熱処理工程に
おける昇温プロセスを制御することにより制御できる。The fine particle film 4 thus formed is two-dimensionally formed in a single layer on the substrate 1. The fine particle film formed as described above can be easily identified by an analysis method such as a scanning electron microscope. Further, the particle size of the fine particles forming the fine particle film can be controlled by the amount of the organometallic complex formed on the substrate before the heat treatment. Further, the variation in the particle size of the fine particles can be controlled by controlling the temperature raising process in the heat treatment step described above.
【0034】本発明の電子放出膜の作製方法を用いるこ
とにより、電子放出膜中の微粒子の粒径を5Å〜500
Åの範囲内に、また、平均粒径のばらつきを±20%の
範囲内に容易に制御し得る。By using the method for producing an electron-emitting film of the present invention, the particle diameter of the fine particles in the electron-emitting film is 5Å to 500.
Within the range of Å and the variation of the average particle size can be easily controlled within the range of ± 20%.
【0035】微粒子の粒径が5Å〜500Åの範囲内に
あることは、微粒子膜4を後述の通電処理し、電子放出
部(領域)5を形成すると電子放出部(領域)5内に形
成された微粒子の粒径及び該微粒子の間隔が、電子放出
に適した粒径及び間隔に形成される様に作用する。さら
に、微粒子膜4の微粒子の平均粒径のばらつきが±20
%の範囲内にあることは、微粒子膜4を通電処理し、電
子放出部(領域)5を形成すると電子放出部(領域)5
内に形成された微粒子の粒径及び該微粒子の間隔のばら
つきが小さくなる様に作用する。When the particle diameter of the fine particles is in the range of 5Å to 500Å, the fine particle film 4 is formed in the electron emitting portion (region) 5 when the electron emitting portion (region) 5 is formed by conducting the electric current treatment described later. The particle size of the fine particles and the interval between the particles act so that the particle size and the interval suitable for electron emission are formed. Furthermore, the variation in the average particle size of the particles of the particle film 4 is ± 20.
Within the range of%, when the fine particle film 4 is energized and the electron emitting portion (region) 5 is formed, the electron emitting portion (region) 5 is formed.
It acts so as to reduce variations in the particle size of the fine particles formed inside and the intervals between the fine particles.
【0036】上記通電処理は、電極2,3間に電圧を印
加することにより、微粒子膜4に電子放出部(領域)5
を形成するものである。尚、通電処理の方法は、電子放
出材料を含む微粒子膜4を通電加熱により、その一部を
高抵抗化して電子放出部(領域)5を形成するものや、
電子放出材料を含む微粒子膜4に通電することにより、
その一部を低抵抗化して電子放出部(領域)5を形成す
るものがあるがいずれを用いても構わない。In the energization process, by applying a voltage between the electrodes 2 and 3, the electron emission portion (region) 5 is formed on the fine particle film 4.
Is formed. The method of energization treatment is to form the electron-emitting portion (region) 5 by electrically heating the fine particle film 4 containing an electron-emitting material to partially increase its resistance.
By energizing the fine particle film 4 containing the electron emitting material,
Some of them have a low resistance to form the electron emitting portion (region) 5, but any of them may be used.
【0037】通電処理時に電極2,3間に印加する電圧
波形は、電極の形状,微粒子膜の材質,基体の材質によ
って適宜設定される。The voltage waveform applied between the electrodes 2 and 3 during the energization process is appropriately set depending on the shape of the electrode, the material of the fine particle film, and the material of the substrate.
【0038】上記通電処理によって、微粒子膜4が構造
変化を起し、電子放出部(領域)が形成される訳である
が、本発明の電子放出膜の作製方法により形成された微
粒子膜は、基体面上に二次元的に一層の状態で形成され
ているため、通電処理時の消費電力が極めて小さく、且
つ通電処理電圧のばらつきが極めて小さくなるため、通
電処理により形成された亀裂、即ち電子放出部(領域)
の幅が均一となり、さらに消費電力が小さいため、通電
処理時の発熱量が極めて小さく、熱的影響を受けないた
め、基体の熱破壊がなく、それによる電子放出部の劣化
がない。The above-mentioned energization treatment causes the fine particle film 4 to undergo a structural change to form an electron emitting portion (region). The fine particle film formed by the method for producing an electron emitting film of the present invention is Since it is two-dimensionally formed in a single layer on the surface of the substrate, the power consumption during energization processing is extremely small and the variation in energization processing voltage is extremely small. Discharge part (area)
Since the width is uniform and the power consumption is small, the amount of heat generated during energization processing is extremely small and is not affected by heat, so that there is no thermal destruction of the substrate and no deterioration of the electron emitting portion.
【0039】以上の様に、本発明の電子放出素子の作製
方法によれば、通電処理により形成された電子放出部
(領域)の幅、及び電子放出部(領域)内の微粒子の粒
径,間隔が電子放出に適した構造、且つ微粒子の粒径,
間隔が均一に形成されるため、電子放出効率に優れ、電
子放出特性が均一な電子放出素子を提供することができ
る。As described above, according to the method of manufacturing the electron-emitting device of the present invention, the width of the electron-emitting portion (region) formed by the energization process, the particle size of the fine particles in the electron-emitting portion (region), The space is suitable for electron emission, and the particle size is
Since the intervals are formed uniformly, it is possible to provide an electron-emitting device having excellent electron emission efficiency and uniform electron emission characteristics.
【0040】本発明により得られる電子放出素子を電子
線発生装置及び画像形成装置の電子源に適用した場合、
素子間の電子放出部(領域)のばらつきがなくなるた
め、均一な電子放出特性を有する電子線発生装置を得ら
れるばかりでなく、画像形成にあたっても輝度むら、表
示のちらつきの極めて少ない画像を形成することができ
る。When the electron-emitting device obtained by the present invention is applied to an electron beam generator and an electron source of an image forming apparatus,
Since there is no variation in the electron emission portion (region) between the elements, it is possible to obtain not only an electron beam generator having uniform electron emission characteristics, but also to form an image with little unevenness in brightness and flickering in display during image formation. be able to.
【0041】また、本発明において、有機金属錯体を熱
処理し電子放出膜を形成する場合、前記微粒子膜は金属
又は金属の化合物からなることが最も好ましい態様であ
るが、前述したような微粒子膜の構成(粒径,粒径のば
らつき等)を形成できれば、有機金属錯体中に電子放出
材からなる微粒子を分散,溶解して形成しても同様な効
果が得られる。In the present invention, in the case of heat-treating an organometallic complex to form an electron emission film, the fine particle film is most preferably made of a metal or a compound of metal. If the composition (particle size, variation in particle size, etc.) can be formed, the same effect can be obtained even if the fine particles made of the electron-emitting material are dispersed and dissolved in the organometallic complex.
【0042】また、有機金属錯体の熱処理時の雰囲気を
制御することにより、金属,金属酸化物及び金属窒化物
等の材料から成る微粒子を任意に作製することができ
る。Further, by controlling the atmosphere during the heat treatment of the organometallic complex, it is possible to arbitrarily produce fine particles made of materials such as metals, metal oxides and metal nitrides.
【0043】更に本発明において、微粒子膜と基体との
密着性を向上させるために、基体上に低軟化点ガラス等
の絶縁層を形成した後、この上に有機金属膜を形成し、
その後、本発明に係る熱処理を行い、更に上記絶縁層の
軟化点以上の温度で処理することにより絶縁層中に微粒
子を部分的に埋設することもできる。これにより、充分
な電子放出量を得るために必要な大きな電圧を印加して
も、電子放出量の変動が極めて小さく、且つ素子破壊の
起こらない電子放出素子とすることができる。Further, in the present invention, in order to improve the adhesion between the fine particle film and the substrate, an insulating layer such as low softening point glass is formed on the substrate, and then an organometallic film is formed thereon.
After that, the heat treatment according to the present invention is performed, and further the treatment is performed at a temperature equal to or higher than the softening point of the insulating layer, so that the fine particles can be partially embedded in the insulating layer. Accordingly, even if a large voltage required to obtain a sufficient electron emission amount is applied, it is possible to obtain an electron-emitting device in which the variation of the electron emission amount is extremely small and the device is not destroyed.
【0044】具体的には、上記絶縁層として例えば酸化
鉛系の低軟化点ガラスであれば、450℃に加熱,約2
0分程度焼成を行なうことにより、低軟化点ガラス上に
配置された微粒子は、低軟化点ガラス中に侵入し、この
中に完全に埋没するか、あるいは少なくとも一部が埋ま
る様に侵入し、いわゆるアンカー(投錨)効果によっ
て、基体に固定され、密着性が極めて向上する。Specifically, if the insulating layer is, for example, a lead oxide-based low softening point glass, it is heated to 450 ° C. and heated to about 2 ° C.
By performing the baking for about 0 minutes, the fine particles arranged on the low softening point glass penetrate into the low softening point glass, and are completely buried or at least partially buried therein. Due to the so-called anchor effect, it is fixed to the substrate and the adhesion is greatly improved.
【0045】微粒子を絶縁層中に完全に埋没するかある
いは一部分のみが埋まる様にするかは、焼成温度を設定
することによって調整することができる。即ち、焼成温
度が高い程、微粒子は絶縁層中に深く侵入し、埋没され
易い。一方、焼成温度が低い程、微粒子は、絶縁層中に
侵入しにくく、一部が露出した形で残りの部分が埋ま
る。Whether the fine particles are completely buried in the insulating layer or only a part thereof is buried can be adjusted by setting the firing temperature. That is, as the firing temperature is higher, the fine particles are more likely to penetrate deeper into the insulating layer and be embedded therein. On the other hand, as the firing temperature is lower, the fine particles are less likely to enter the insulating layer, and the remaining portion is filled with the exposed portion.
【0046】この場合、絶縁層の最表面上の微粒子が少
なくとも一部分が露出していなければならないが、その
下層に完全に埋没した微粒子が存在していてもかまわな
い。In this case, at least a part of the fine particles on the outermost surface of the insulating layer must be exposed, but completely buried fine particles may be present in the lower layer.
【0047】また、絶縁層中に埋まっている微粒子の最
深部の深さは、微粒子の粒子径の0.2〜3倍であるこ
とが好ましく、更には0.5〜1.5倍であることが望
ましい。なぜならば、この範囲を超えて、微粒子が絶縁
層中により深く存在している場合、通電処理により、電
子放出部を形成すると、微粒子の厚みが厚いため、通電
処理時に非常に大きな電流が流れて発熱するため、基体
の破壊による電子放出部の劣化が発生するからである。
逆により浅い場合には、いわゆるアンカー効果が認めら
れず、密着性の向上が著しく認められないからである。The depth of the deepest part of the fine particles embedded in the insulating layer is preferably 0.2 to 3 times, more preferably 0.5 to 1.5 times the particle diameter of the fine particles. Is desirable. This is because, if the fine particles are present deeper in the insulating layer beyond this range, a very large current will flow during the current-carrying process when the electron-emitting portion is formed by the current-carrying process because the thickness of the fine particles is large. This is because heat is generated, and the electron emitting portion is deteriorated due to the destruction of the substrate.
On the contrary, when the depth is shallower, the so-called anchor effect is not recognized, and the adhesiveness is not significantly improved.
【0048】更に、微粒子を絶縁層中に完全に埋没させ
た後、エッチング処理を行ない、微粒子の一部を絶縁層
表面に露出させてもよい。Further, after the fine particles are completely buried in the insulating layer, etching treatment may be performed to expose a part of the fine particles on the surface of the insulating layer.
【0049】[0049]
【実施例及び比較例】以下に実施例,比較例を示し本発
明を詳しく説明する。EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples.
【0050】実施例1 本実施例では、本発明に係る有機金属膜の熱処理を図1
に示されるような温度プロファイルにより行ない図27
〜図29に示した構成を有する電子放出素子を作製し
た。 Example 1 In this example, the heat treatment of the organic metal film according to the present invention is performed as shown in FIG.
The temperature profile shown in FIG.
~ An electron-emitting device having the structure shown in Fig. 29 was produced.
【0051】本実施例における作製工程を図2を用いて
説明する。 絶縁性基体21として石英基板を用い、これを有機
溶剤により充分に洗浄後、該基体21面上に、電極2
2,23を形成した(図2(a)参照)。電極の材料と
して、Au金属を用いた。電極間隔Gは2μmとし、電
極の長さ(紙面奥行き方向)を500μm、その厚さを
1000Åとした。 基体21上に有機パラジウム錯体(融点:100
℃,分解温度:220℃)の酢酸ブチル溶液(Pd1w
t%含有)をスピナー塗布した後、図1に示した温度プ
ロファイルで空気中で加熱処理し、酸化パラジウム微粒
子(平均粒径60Å)からなる微粒子膜24を形成し
た。ここで微粒子膜24の長さ(紙面奥行き方向)を3
00μmとして、電極22,23のほぼ中央に配置した
(図2(b)参照)。 次に、電極22と電極23の間に電圧を印加し、微
粒子膜24を通電処理(フォーミング処理)することに
より電子放出領域25を形成した(図2(c)参照)。
フォーミング処理の電圧波形を図3に示す。The manufacturing process in this embodiment will be described with reference to FIGS. A quartz substrate is used as the insulative base 21, and after thoroughly cleaning it with an organic solvent, the electrode 2 is formed on the surface of the base 21.
2 and 23 were formed (see FIG. 2A). Au metal was used as the material of the electrodes. The electrode interval G was 2 μm, the length of the electrodes (in the depth direction of the paper surface) was 500 μm, and the thickness thereof was 1000 Å. Organic palladium complex (melting point: 100
℃, decomposition temperature: 220 ℃ butyl acetate solution (Pd1w
After containing t%) by spinner coating, heat treatment was performed in air according to the temperature profile shown in FIG. 1 to form a fine particle film 24 made of palladium oxide fine particles (average particle size 60Å). Here, the length of the fine particle film 24 (the depth direction of the paper surface) is set to 3
The thickness was set to 00 μm, and the electrodes 22 and 23 were arranged substantially in the center (see FIG. 2B). Next, a voltage was applied between the electrode 22 and the electrode 23 to energize the fine particle film 24 (forming process) to form the electron emission region 25 (see FIG. 2C).
FIG. 3 shows the voltage waveform of the forming process.
【0052】図3中、T1 及びT2 は電圧波形のパルス
幅とパルス間隔であり、本実施例ではT1 を1.0ミリ
秒、T2 を10ミリ秒とした。また、フォーミング処理
は約1×10-6torrの真空雰囲気下で行った。In FIG. 3, T 1 and T 2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T 1 is 1.0 ms and T 2 is 10 ms. The forming process was performed in a vacuum atmosphere of about 1 × 10 −6 torr.
【0053】この様にして形成した電子放出領域25を
走査型電子顕微鏡で観察したところ、酸化パラジウム微
粒子からなる微粒子膜24間に平均粒径30Åのパラジ
ウム微粒子が形成されていた。When the electron emission region 25 thus formed was observed by a scanning electron microscope, palladium fine particles having an average particle diameter of 30Å were formed between the fine particle films 24 made of palladium oxide fine particles.
【0054】上記工程で同様の素子を500素子作製
し、図4に示される評価装置を用いて電子放出特性を測
定した。In the above process, 500 similar devices were manufactured, and the electron emission characteristics were measured by using the evaluation apparatus shown in FIG.
【0055】図4において、31は素子に電圧を印加す
るための電源、30は素子電流Ifを測定するための電
流計、34は素子より発生する放出電流Ieを測定する
ためのアノード電極、33はアノード電極34に電圧を
印加するための高圧電源、32は放出電流を測定するた
めの電流計である。ここで、上記素子電流とは、電流計
30によって測定される電流量であり、また、上記放出
電流とは、電流計32により測定される電流量である。
電子放出素子の上記素子電流、放出電流の測定にあたっ
ては、素子電極22,23に電源31と電流計30とを
接続し、該電子放出素子の上方に電源33と電流計32
とを接続したアノード電極34を配置し、真空度1×1
0-7torrの環境下で行う。In FIG. 4, 31 is a power supply for applying a voltage to the element, 30 is an ammeter for measuring the element current If, 34 is an anode electrode for measuring the emission current Ie generated from the element, 33 Is a high voltage power supply for applying a voltage to the anode electrode 34, and 32 is an ammeter for measuring the emission current. Here, the element current is the amount of current measured by the ammeter 30, and the emission current is the amount of current measured by the ammeter 32.
To measure the device current and the emission current of the electron-emitting device, a power supply 31 and an ammeter 30 are connected to the device electrodes 22 and 23, and a power supply 33 and an ammeter 32 are provided above the electron-emitting device.
Arrange the anode electrode 34 connected to and vacuum degree 1 × 1
It is performed in an environment of 0 -7 torr.
【0056】本実施例では、素子電圧(Vf)=14
V,アノード電圧(Va)=2kV下での各素子の素子
電流(If),放出電流(Ie)及び電子放出効率(η
=Ie/If)の頻度分布を測定した。その結果を図5
に示す。尚、図5(a)は素子電流の頻度分布、図5
(b)は放出電流の頻度分布、図5(c)は電子放出効
率の頻度分布を示している。In this embodiment, the element voltage (Vf) = 14
Device current (If), emission current (Ie), and electron emission efficiency (η) of each device under V, anode voltage (Va) = 2 kV
= Ie / If) frequency distribution was measured. The result is shown in Fig. 5.
Shown in. 5A is a frequency distribution of the device current,
FIG. 5B shows the frequency distribution of the emission current, and FIG. 5C shows the frequency distribution of the electron emission efficiency.
【0057】比較例1 実施例1において、有機パラジウム錯体の熱処理を図6
に示される温度プロファイルにより行った以外は全く同
様にして電子放出素子を500素子作製し、実施例1と
同様にして電子放出特性を測定した。その結果を図7に
示す。図7と実施例1の測定結果の図5との比較から明
らかなように、熱処理時に有機パラジウム錯体の融点温
度で一定期間保持することにより、素子間の電子放出特
性のばらつきを低減できることが理解される。 Comparative Example 1 In Example 1, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 electron-emitting devices were manufactured in exactly the same manner except that the temperature profile shown in 1 was used, and the electron-emitting characteristics were measured in the same manner as in Example 1. The result is shown in FIG. 7. As is clear from a comparison between FIG. 7 and FIG. 5 of the measurement results of Example 1, it is understood that by maintaining the melting point temperature of the organopalladium complex for a certain period during the heat treatment, it is possible to reduce variations in electron emission characteristics between devices. To be done.
【0058】また、本発明者らが行った数多くの実験で
は、有機金属の材料や基体上への有機金属の形成量によ
らず、上記温度保持期間が1分以上であればほぼ均一な
素子特性が得られた。Further, in many experiments conducted by the inventors, regardless of the material of the organic metal or the amount of the organic metal formed on the substrate, if the temperature holding period is 1 minute or more, a substantially uniform element is obtained. The characteristics were obtained.
【0059】比較例2 実施例1において、有機パラジウム錯体の熱処理を図8
に示される温度プロファイルにより行った以外は全く同
様にして電子放出素子を500素子作製し、実施例1と
同様にして電子放出特性を測定した。その結果を図9に
示す。 Comparative Example 2 In Example 1, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 electron-emitting devices were manufactured in exactly the same manner except that the temperature profile shown in 1 was used, and the electron-emitting characteristics were measured in the same manner as in Example 1. The result is shown in FIG.
【0060】図9と実施例1の測定結果の図5との比較
から明らかなように、熱処理時における室温から有機パ
ラジウム錯体の融点温度までの昇温速度が速い方が、素
子の均一性にとって、より一層有効に作用することが理
解される。As is clear from the comparison between FIG. 9 and FIG. 5 showing the measurement results of Example 1, the higher the rate of temperature increase from room temperature to the melting point of the organopalladium complex during heat treatment, the better the uniformity of the device. It is understood that it works even more effectively.
【0061】また、本発明者らが行った数多くの実験で
は、有機金属の材料によらず、有機金属の融点±10℃
の温度以上且つ有機金属の分解温度未満の温度Taまで
の昇温速度が1℃/分以上、更に好ましくは、この昇温
速度が、上記温度Taから有機金属の分解温度以上の温
度Tbまでの昇温速度以上であれば、より一層均一な素
子特性が得られた。In many experiments conducted by the present inventors, the melting point of the organic metal is ± 10 ° C. regardless of the material of the organic metal.
At a temperature of 1 ° C./min or more to a temperature Ta which is equal to or higher than the temperature of the organic metal and lower than the decomposition temperature of the organic metal, and more preferably from the temperature Ta to a temperature Tb higher than the decomposition temperature of the organic metal. If the heating rate is higher than the heating rate, more uniform device characteristics can be obtained.
【0062】実施例2 本実施例の電子放出素子は次の方法で作製された。 実施例1と同様にして絶縁性基体上に一対の電極を
作製した。 実施例1と同様にして、基体上に有機パラジウム錯
体の酢酸ブチル溶液をスピナー塗布した後、還元雰囲気
(水素ガスとN2ガスの混合ガス)中で図1に示した温
度プロファイルを用い加熱処理を行ない、金属パラジウ
ム微粒子(平均粒径30Å)からなる微粒子膜を形成し
た。微粒子膜のシート抵抗値は3×103Ω/□であっ
た。 上記で作製した金属パラジウム微粒子膜に図3に
示したような電圧波形のフォーミング処理を施すことに
より、本実施例の電子放出素子を作製した。 Example 2 The electron-emitting device of this example was manufactured by the following method. A pair of electrodes was prepared on the insulating substrate in the same manner as in Example 1. In the same manner as in Example 1, a butyl acetate solution of an organopalladium complex was applied onto the substrate by spinner, and then heat treatment was performed in a reducing atmosphere (a mixed gas of hydrogen gas and N 2 gas) using the temperature profile shown in FIG. Was carried out to form a fine particle film made of fine metal palladium particles (average particle size 30Å). The sheet resistance of the fine particle film was 3 × 10 3 Ω / □. An electron-emitting device of this example was produced by subjecting the metal palladium fine particle film produced above to a forming process with a voltage waveform as shown in FIG.
【0063】上記工程で同様の素子を500素子作製
し、実施例1と同様な評価をしたところ、素子電流,放
出電流,電子放出効率共に図5とほぼ同等な頻度分布と
なった。When 500 similar devices were manufactured in the above process and evaluated in the same manner as in Example 1, the device current, emission current, and electron emission efficiency all had frequency distributions substantially equal to those in FIG.
【0064】実施例3 本実施例の電子放出素子は以下の方法で作製された。 実施例1と同様にして絶縁性基体上に一対の電極を
作製した。 実施例1と同様にして、基体上に有機パラジウム錯
体の酢酸ブチル溶液をスピナー塗布した後、真空槽にN
2 ガスを4×10-2torr導入し、RF放電を誘起し
て窒素プラズマを起こした。前記N2 プラズマ雰囲気下
において、図1に示した温度プロファイルを用い加熱処
理を行ない、窒化パラジウム微粒子からなる微粒子膜を
形成した。微粒子膜のシート抵抗は2×105 Ω/□で
あった。 上記で作製した微粒子膜に図3に示したような電
圧波形のフォーミング処理を施すことにより、本実施例
の電子放出素子を作製した。 Example 3 The electron-emitting device of this example was manufactured by the following method. A pair of electrodes was prepared on the insulating substrate in the same manner as in Example 1. In the same manner as in Example 1, a substrate was spin coated with a solution of an organopalladium complex in butyl acetate, and then N was placed in a vacuum chamber.
2 gas was introduced at 4 × 10 -2 torr, and RF discharge was induced to generate nitrogen plasma. In the N 2 plasma atmosphere, heat treatment was performed using the temperature profile shown in FIG. 1 to form a fine particle film made of palladium nitride fine particles. The sheet resistance of the fine particle film was 2 × 10 5 Ω / □. An electron-emitting device of this example was manufactured by subjecting the above-prepared fine particle film to a forming process with a voltage waveform as shown in FIG.
【0065】上記工程で同様の素子を500素子作製
し、実施例1と同様な評価を行ったところ、素子電流,
放出電流,電子放出効率共に図5とほぼ同様な頻度分布
となった。In the above process, 500 similar devices were produced and evaluated in the same manner as in Example 1. The device current,
Both the emission current and the electron emission efficiency have almost the same frequency distribution as in FIG.
【0066】実施例4 本実施例の電子放出素子は次の方法で作製された(作製
工程は図2を参照)。 実施例1と同様にして絶縁性
基体21上に一対の電極22,23を作製した。 有機白金錯体(融点:190℃,分解温度:400
℃)の酢酸ブチル溶液をスピナー塗布した後、図10に
示す温度プロファイルで空気中で加熱処理し、白金微粒
子(粒径20Å〜100Å)からなる微粒子膜24を形
成した。ここで微粒子膜24の長さ(紙面奥行き方向)
を300μmとして、電極22,23のほぼ中央に配置
した。 次に電極22と電極23の間に電圧を印加し、微粒
子膜24をフォーミング処理することにより電子放出領
域25を形成した。 Example 4 The electron-emitting device of this example was manufactured by the following method (refer to FIG. 2 for manufacturing process). A pair of electrodes 22 and 23 were formed on the insulating substrate 21 in the same manner as in Example 1. Organic platinum complex (melting point: 190 ° C, decomposition temperature: 400
C.) butyl acetate solution was applied by a spinner and then heat-treated in air according to the temperature profile shown in FIG. 10 to form a fine particle film 24 of platinum fine particles (particle diameter 20Å to 100Å). Here, the length of the fine particle film 24 (the depth direction of the paper surface)
Was set to be 300 μm, and the electrodes 22 and 23 were arranged substantially in the center. Next, a voltage was applied between the electrode 22 and the electrode 23, and the fine particle film 24 was subjected to a forming treatment to form the electron emission region 25.
【0067】フォーミング処理は約1×10-6torr
の真空雰囲気下、10Vの直流電圧連続印加により行っ
た。The forming process is about 1 × 10 -6 torr
In a vacuum atmosphere of, a DC voltage of 10 V was continuously applied.
【0068】上記工程で同様の素子を500素子作製
し、1×10-7torrの真空下にて実施例1と同様の
評価を行ったところ、図11に示されるような結果が得
られた。尚、図11(a)は素子電流の頻度分布、図1
1(b)は放出電流の頻度分布、図11(c)は電子放
出効率の頻度分布を示している。When 500 similar devices were manufactured in the above process and evaluated in the same manner as in Example 1 under a vacuum of 1 × 10 −7 torr, the results shown in FIG. 11 were obtained. . Incidentally, FIG. 11A shows the frequency distribution of the device current,
1 (b) shows the frequency distribution of the emission current, and FIG. 11 (c) shows the frequency distribution of the electron emission efficiency.
【0069】以上の結果から、本実施例の各素子はほぼ
均一な素子特性を有している。From the above results, each element of this example has almost uniform element characteristics.
【0070】実施例5 本実施例の電子放出素子は次の方法で作製された(作製
工程は図2を参照)。 実施例1と同様にして絶縁性基体21上に一対の電
極22,23を作製した。 有機ルテニウム錯体(融点:約310℃,分解温
度:約420℃)の酢酸ブチル溶液をスピナー塗布した
後、図12に示す温度プロファイルで空気中で加熱処理
し、ルテニウム微粒子(粒径20Å〜100Å)からな
る微粒子膜24を形成した。 上記で作製した微粒子膜24に1×10-6tor
rの真空雰囲気中で10Vの直流電圧連続印加によるフ
ォーミング処理を施すことにより、電子放出素子を作製
した。 Example 5 The electron-emitting device of this example was produced by the following method (see FIG. 2 for production steps). A pair of electrodes 22 and 23 were formed on the insulating substrate 21 in the same manner as in Example 1. A solution of an organic ruthenium complex (melting point: about 310 ° C., decomposition temperature: about 420 ° C.) in butyl acetate was applied by spinner, and then heat-treated in air according to the temperature profile shown in FIG. 12, ruthenium fine particles (particle size 20Å to 100Å) A fine particle film 24 of was formed. 1 × 10 −6 torr on the fine particle film 24 produced above
An electron-emitting device was manufactured by performing a forming process by continuously applying a DC voltage of 10 V in a vacuum atmosphere of r.
【0071】上記工程で同様の素子を500素子作製
し、実施例4と同様な評価を行ったところ、素子電流,
放出電流,電子放出効率共に図11とほぼ同等な頻度分
布となった。In the above process, 500 similar devices were produced, and the same evaluation as in Example 4 was carried out.
Both the emission current and the electron emission efficiency have almost the same frequency distribution as in FIG.
【0072】実施例6 本実施例では、本発明により作製した電子放出膜(微粒
子膜)の均一性についての評価を行った。 Example 6 In this example, the uniformity of the electron emission film (fine particle film) produced according to the present invention was evaluated.
【0073】本実施例における微粒子膜の作製方法を図
13の作製工程図を用いて説明する。 絶縁性基体131として石英基板を用い、これを有
機溶剤により充分に洗浄後、金属クロム132を200
Åの厚みで蒸着した(図13(a)参照)。その後、ポ
ジ型レジストで200μ×300μのパターンを形成し
Crをウェットエッチした後、レジストを剥離し、20
0μ×300μmの穴のあいたクロムマスク132’を
形成した。 基体131上に有機パラジウム錯体の酢酸ブチル溶
液をスピナー塗布した後、図1に示した温度プロファイ
ルで空気中で加熱処理をした。この操作を2度繰り返し
て、酸化パラジウム微粒子からなる微粒子膜133を形
成した(図13(c)参照)。次に、Crをエッチアウ
トし、パターン状の酸化パラジウム微粒子133’を形
成した。A method of manufacturing the fine particle film in this embodiment will be described with reference to the manufacturing process chart of FIG. A quartz substrate is used as the insulative substrate 131, and the quartz substrate is thoroughly washed with an organic solvent.
It was vapor-deposited with a thickness of Å (see FIG. 13 (a)). After that, a 200 μ × 300 μ pattern is formed with a positive resist, the Cr is wet-etched, and then the resist is peeled off.
A chrome mask 132 ′ having a hole of 0 μ × 300 μm was formed. After spin coating a butyl acetate solution of an organic palladium complex on the base 131, heat treatment was performed in air according to the temperature profile shown in FIG. This operation was repeated twice to form a fine particle film 133 made of fine palladium oxide particles (see FIG. 13C). Then, Cr was etched out to form patterned palladium oxide fine particles 133 ′.
【0074】この様にして作製したパターン状酸化パラ
ジウム微粒子膜の膜厚を触針式膜厚計α−ステップ25
0(TENCOR製)にて測定したところ、図14の様
になった。図14において、dの値が20Å以上のもの
を「うねり」と称して、40μmスキャン中の「うね
り」の数を、上記作製法と同様にして作製した500個
のパターン状酸化パラジウム微粒子膜について測定し、
その頻度を図15(a)に示す。The thickness of the patterned palladium oxide fine particle film thus produced was measured by a stylus type film thickness meter α-step 25.
When measured with 0 (manufactured by TENCOR), the result is as shown in FIG. In FIG. 14, those having a value of d of 20 Å or more are referred to as “waviness”, and the number of “waviness” in a 40 μm scan is measured for 500 patterned palladium oxide fine particle films produced in the same manner as in the above production method. Measure
The frequency is shown in FIG.
【0075】比較例3 実施例6において、有機パラジウム錯体の熱処理を図6
に示した温度プロファイルにより行った以外は全く同様
にしてパターン状酸化パラジウム微粒子膜を500個作
製し、実施例6と同様にして40μmスキャンあたりの
「うねり」の頻度を測定した。 Comparative Example 3 In Example 6, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 patterned palladium oxide fine particle films were prepared in exactly the same manner except that the temperature profile shown in FIG. 5 was used, and the frequency of “waviness” per 40 μm scan was measured in the same manner as in Example 6.
【0076】その結果を図15(b)に示す。The results are shown in FIG. 15 (b).
【0077】比較例4 実施例6において、有機パラジウム錯体の熱処理を図8
に示した温度プロファイルにより行った以外は全く同様
にしてパターン状酸化パラジウム微粒子膜を500個作
製し、実施例6と同様にして40μmスキャンあたりの
「うねり」の頻度を測定した。 Comparative Example 4 In Example 6, the heat treatment of the organopalladium complex was performed as shown in FIG.
500 patterned palladium oxide fine particle films were prepared in exactly the same manner except that the temperature profile shown in FIG. 5 was used, and the frequency of “waviness” per 40 μm scan was measured in the same manner as in Example 6.
【0078】その結果を図15(c)に示す。The results are shown in FIG. 15 (c).
【0079】実施例6及び比較例3,4の結果から明ら
かなように、本発明により作製される微粒子膜は平滑性
に富み、ほぼ均一な膜厚に形成されており、パターニン
グによってもその均一性が保持される。As is clear from the results of Example 6 and Comparative Examples 3 and 4, the fine particle film produced according to the present invention has excellent smoothness and is formed to have a substantially uniform film thickness. Sex is retained.
【0080】実施例7 実施例2〜5の作製方法において、実施例6と同様に
して金属あるいは金属化合物からなる微粒子膜をパター
ン化し、パターン状微粒子膜を500個作製し、実施例
6と同様にして40μmあたりの「うねり」の頻度を測
定したところ、実施例6と同様の均一性が得られた。 Example 7 In the manufacturing method of Examples 2 to 5, the fine particle film made of a metal or a metal compound was patterned in the same manner as in Example 6 to prepare 500 patterned fine particle films, and the same as in Example 6. When the frequency of “waviness” per 40 μm was measured, the same uniformity as in Example 6 was obtained.
【0081】実施例8 本実施例の微粒子膜は以下の方法で作製された。 実施例6と同様にして絶縁性基体上にクロムマスク
を形成した。 基体上に有機パラジウム錯体の酢酸ブチル溶液をス
ピナー塗布した後、図1に示した温度プロファイルで空
気中で加熱処理をした。本実施例では、上記操作を1〜
4回行うことにより、4種類の微粒子膜を形成し、その
後Crをエッチアウトし、パターン状酸化パラジウム微
粒子膜とした。 Example 8 The fine particle film of this example was produced by the following method. A chrome mask was formed on the insulating substrate in the same manner as in Example 6. A butyl acetate solution of an organic palladium complex was applied onto the substrate by a spinner, and then heat treatment was performed in the air according to the temperature profile shown in FIG. In this embodiment, the above operations are
By carrying out four times, four kinds of fine particle films were formed, and then Cr was etched out to obtain a patterned palladium oxide fine particle film.
【0082】この様にして作製した4種類のパターン状
酸化パラジウム微粒子膜をSEM及びSTMにより観察
したところ、各々の微粒子膜は全て一層であったが、そ
の膜厚は図16に示される結果となった。図16から、
有機パラジウム錯体の塗布,熱処理を繰り返すことによ
り、微粒子の粒径を大きくでき、粒径を制御できること
が確認された。When the four types of patterned palladium oxide fine particle films thus produced were observed by SEM and STM, each fine particle film was a single layer, but the film thickness was as shown in FIG. became. From FIG.
It was confirmed that the particle size of the fine particles can be increased and the particle size can be controlled by repeating the application of the organic palladium complex and the heat treatment.
【0083】実施例9 本実施例の電子放出素子の通電処理前の平面図とその断
面図を図17に示し、通電処理後の平面図とその断面図
を図18に示す。図17及び図18において171は絶
縁性基体、172及び173は電極、174は微粒子
膜、175は電子放出部(領域)を示す。本実施例の電
子放出素子は、以下の様に作製された。 絶縁性基体171として石英基板を用い、有機溶剤
等により充分洗浄し、真空蒸着技術、フォトリソグラフ
ィー技術により電極172,173を形成した。電極の
材料としては導電性を有するものであればどのようなも
のであっても構わないが、本実施例では、ニッケル(N
i)金属を用いて形成した。電極間隔は2μmとし、電
極の長さは300μmとし、膜厚は1000Åとした。 次に、有機ルテニウム錯体を酢酸nブチル溶剤に1
0wt%の割合で分散,溶解した溶液を用い、有機ルテ
ニウム錯体溶液を塗布したくないところには、テープ、
又はレジスト膜を設け、その後、スピナー法で絶縁性基
体171上に塗布する。次に、テープ又はレジスト膜を
剥離することにより所定の位置に有機ルテニウム膜を形
成する。ついで、図12に示した温度プロファイルの様
に有機ルテニウム錯体の融点が約310℃、分解温度が
約420℃であるため、融点から分解温度以下の温度と
保持時間を350℃−30minとし、分解温度以上の
温度と保持時間を480℃−20minとし大気中で熱
処理し、ルテニウム(Ru)微粒子(粒径60Å〜80
Å,平均粒径70Å,平均粒径のばらつき±14%)か
らなる微粒子膜174を形成した。 次に、電極172及び173の間に電圧を印加し微
粒子膜174を通電処理し、電子放出部(領域)175
を作成したところ、電子放出部(領域)175の幅約
0.1μm、電子放出部(領域)175内に形成された
微粒子の粒径30Å〜40Å、微粒子の間隔5Å〜20
Åで形成された。 次に、上記電子放出素子を1×10-5torrの真
空下にて、電極172及び173の間に電圧14Vを印
加したところ、複数の素子において良好な電子放出特性
が確認され、更には各素子間の電子放出素子のばらつき
が非常に少なかった。 Embodiment 9 FIG. 17 shows a plan view and a cross-sectional view of the electron-emitting device of this embodiment before the energization process is performed, and FIG. 18 is a plan view after the energization process and a cross-sectional view thereof. 17 and 18, 171 is an insulating substrate, 172 and 173 are electrodes, 174 is a fine particle film, and 175 is an electron emitting portion (region). The electron-emitting device of this example was manufactured as follows. A quartz substrate was used as the insulating base 171 and was sufficiently washed with an organic solvent or the like, and electrodes 172 and 173 were formed by a vacuum deposition technique and a photolithography technique. Any material may be used as the material of the electrodes as long as it has conductivity, but in the present embodiment, nickel (N
i) Formed using a metal. The electrode interval was 2 μm, the electrode length was 300 μm, and the film thickness was 1000 Å. Next, the organic ruthenium complex was added to a solvent of n-butyl acetate to prepare 1
Use a solution that is dispersed and dissolved at a ratio of 0 wt% and use a tape on a place where the organic ruthenium complex solution is not desired to be applied.
Alternatively, a resist film is provided and then coated on the insulating base 171 by a spinner method. Next, the tape or the resist film is peeled off to form an organic ruthenium film at a predetermined position. Next, as shown in the temperature profile shown in FIG. 12, since the melting point of the organic ruthenium complex is about 310 ° C. and the decomposition temperature is about 420 ° C., the temperature from the melting point to the decomposition temperature or lower and the holding time are 350 ° C.-30 min. Ruthenium (Ru) fine particles (particle size 60Å to 80
Å, average particle size 70 Å, average particle size variation ± 14%) was formed. Next, a voltage is applied between the electrodes 172 and 173 to energize the fine particle film 174, and an electron emitting portion (region) 175 is applied.
The width of the electron emitting portion (region) 175 was about 0.1 μm, the particle diameter of the fine particles formed in the electron emitting portion (region) 175 was 30 Å to 40 Å, and the space between the fine particles was 5 Å to 20.
Formed by Å. Next, when a voltage of 14 V was applied between the electrodes 172 and 173 of the electron-emitting device under a vacuum of 1 × 10 −5 torr, good electron-emitting characteristics were confirmed in a plurality of devices, and further, The variation of the electron-emitting devices among the devices was very small.
【0084】以上の様に、本発明により作製される本実
施例の電子放出素子は、その電子放出膜(微粒子膜)中
の微粒子が、電子放出に適した粒径及び間隔に制御され
ると共に、その平均粒径のばらつきが小さいため、通電
処理電圧のばらつきが極めて小さく、電子放出部の幅が
均一となり、優れた電子放出特性が得られると共に、複
数の素子間において、その特性が均一となる。As described above, in the electron-emitting device of this embodiment manufactured according to the present invention, the particles in the electron-emitting film (particle film) are controlled to have a particle size and interval suitable for electron emission. Since the variation in the average particle size is small, the variation in the energization processing voltage is extremely small, the width of the electron emitting portion is uniform, excellent electron emission characteristics are obtained, and the characteristics are uniform among a plurality of elements. Become.
【0085】実施例10 本実施例の電子放出素子は、実施例9において微粒子膜
174の形成に、有機ルテニウム錯体を酢酸nブチル溶
剤に20wt%の割合で分散,溶解した溶液を用いた以
外は、実施例9と同様に作製した。 Example 10 The electron-emitting device of this example is different from that of Example 9 in that the fine particle film 174 was formed by using a solution in which an organic ruthenium complex was dispersed and dissolved in a solvent of n-butyl acetate at a ratio of 20 wt%. Was manufactured in the same manner as in Example 9.
【0086】本実施例の電子放出素子は微粒子膜174
中のルテニウム(Ru)微粒子の粒径は130Å〜18
0Å(平均粒径155Å,平均粒径のばらつき±16
%)であり、通電処理により作成された電子放出部(領
域)175の幅約0.2μm、電子放出部(領域)17
5内に形成された微粒子の粒径60Å〜90Å、微粒子
の間隔5Å〜30Åで形成された。本実施例の電子放出
素子を実施例9と同様に電子放出させたところ、実施例
9と同様に良好な結果を得た。The electron-emitting device of this embodiment has a fine particle film 174.
The particle size of the ruthenium (Ru) particles is 130Å-18
0Å (average particle size 155Å, average particle size variation ± 16
%), The width of the electron-emitting portion (region) 175 formed by the energization process is about 0.2 μm, and the electron-emitting portion (region) 17 is about 0.2 μm.
The fine particles formed in No. 5 had a particle size of 60 Å to 90 Å and an interval of the fine particles of 5 Å to 30 Å. When the electron-emitting device of this example was made to emit electrons in the same manner as in Example 9, good results were obtained as in Example 9.
【0087】比較例5 実施例9において、微粒子膜をガスデポジション法によ
りルテニウム(Ru)微粒子の粒径30Å〜300Å
(平均粒径165Å,平均粒径のばらつき±80%)の
範囲で複数層形成した以外、実施例9と同様にして電子
放出素子を作製した。 Comparative Example 5 In Example 9, the fine particle film was formed by the gas deposition method, and the particle diameter of ruthenium (Ru) fine particles was 30Å to 300Å.
An electron-emitting device was produced in the same manner as in Example 9 except that a plurality of layers were formed in the range of (average particle size 165Å, average particle size variation ± 80%).
【0088】本比較例で作製した電子放出素子の断面図
を図19に示す。FIG. 19 shows a sectional view of the electron-emitting device manufactured in this comparative example.
【0089】本素子は通電処理により電子放出部(領
域)の幅が約0.1μmから約0.25μmとばらつい
ており、電子放出部(領域)内に形成された微粒子の粒
径10Å〜160Å、微粒子の間隔5Å〜60Åで形成
された。In this device, the width of the electron emission portion (region) varies from about 0.1 μm to about 0.25 μm due to the energization process, and the particle diameter of the fine particles formed in the electron emission portion (region) is 10 Å to 160 Å. The fine particles were formed with an interval of 5Å to 60Å.
【0090】本素子を実施例9と同様に電子放出させた
ところ、電子の放出は得られたが、良好な特性を得るこ
とができなかった。When electrons were emitted from this device in the same manner as in Example 9, although emission of electrons was obtained, good characteristics could not be obtained.
【0091】以上の様に、有機金属膜を用いずに本発明
に係る熱処理を行っても、良好な電子放出膜(微粒子
膜)が得られないことがわかる。As described above, it is understood that a good electron emission film (fine particle film) cannot be obtained even if the heat treatment according to the present invention is performed without using the organometallic film.
【0092】実施例11 本実施例の電子放出膜(微粒子膜)として有機パラジウ
ム錯体を用いて、酸化パラジウム微粒子膜を作製した。
以下にその作製手順を述べる。 酢酸,硝酸,パラジウムブラックの混合物を硝酸の
すべてが消費されるまで還流する。その後、反応パラジ
ウムを濾過で除き、減圧下で酢酸を留去し残渣をジクロ
ロメタン−ヘキサンより再結晶して、赤色微結晶[Pd
(OAc)2 ]6H2 Oを得た。DTAより分解温度を
測定したところ235℃であった。 で得た微結晶を酢酸n−ブチルで溶解し、Pd含
量がおよそ10g/lの有機パラジウム溶液を作製し
た。 の溶液を絶縁性基体上にスピナー塗布した後、図
1に示した温度プロファイルで空気中で加熱処理し、酸
化パラジウム微粒子(平均粒径60Å)からなる微粒子
膜を形成した。 Example 11 A palladium oxide fine particle film was prepared by using an organic palladium complex as the electron emission film (fine particle film) of this example.
The manufacturing procedure will be described below. Reflux a mixture of acetic acid, nitric acid and palladium black until all of the nitric acid is consumed. Thereafter, the reaction palladium was removed by filtration, acetic acid was distilled off under reduced pressure, and the residue was recrystallized from dichloromethane-hexane to give red fine crystals [Pd
(OAc) 2 ] 6 H 2 O was obtained. The decomposition temperature measured by DTA was 235 ° C. The microcrystals obtained in 1. were dissolved in n-butyl acetate to prepare an organopalladium solution having a Pd content of about 10 g / l. After spin-coating the solution of (1) on an insulating substrate, it was heat-treated in air according to the temperature profile shown in FIG. 1 to form a fine particle film composed of palladium oxide fine particles (average particle size 60 Å).
【0093】図20は上記作製手順で作製したPdO微
粒子膜の断面のSEM(走査型電子顕微鏡)写真の模式
図である。FIG. 20 is a schematic view of an SEM (scanning electron microscope) photograph of a cross section of the PdO fine particle film produced by the above-described production procedure.
【0094】同図において、201は絶縁性基体である
ところの石英基板、202はPdO微粒子である。Pd
O微粒子の粒径は図20から判断したところ、50Å〜
70Åであった。In the figure, 201 is a quartz substrate which is an insulating substrate, and 202 is PdO fine particles. Pd
Judging from FIG. 20, the particle size of O fine particles is 50Å ~
It was 70Å.
【0095】本実施例で作製した微粒子膜の膜厚および
形状を触針式膜厚計α−ステップ250(TENCOR
製)にて測定したところ、図21に示すような結果が得
られた。同図においてスキャン幅25μm以降が微粒子
膜部分を示している。また、該微粒子膜の4端子法によ
るシート抵抗は5.0×104 Ω/□であった。The thickness and shape of the fine particle film produced in this example was measured by a stylus type film thickness meter α-step 250 (TENCOR).
21), the results shown in FIG. 21 were obtained. In the figure, the scan width of 25 μm or later indicates the fine particle film portion. The sheet resistance of the fine particle film by the four-terminal method was 5.0 × 10 4 Ω / □.
【0096】実施例12 実施例11において、空気中での加熱処理を、図1に示
した温度プロファイル中、有機パラジウムの分解温度
(235℃)以上での保持温度を300℃にかえて26
0℃で行った以外は、実施例11と同様にして微粒子膜
を作製した。 Example 12 In Example 11, the heat treatment in air was carried out by changing the holding temperature above the decomposition temperature (235 ° C.) of organopalladium to 300 ° C. in the temperature profile shown in FIG.
A fine particle film was produced in the same manner as in Example 11 except that the operation was performed at 0 ° C.
【0097】実施例11と同様にして、微粒子膜の膜厚
及び形状を測定したところ、実施例11とほぼ同様であ
った。When the thickness and shape of the fine particle film were measured in the same manner as in Example 11, it was almost the same as in Example 11.
【0098】また、微粒子膜のシート抵抗は5.8×1
04 Ω/□であった。The sheet resistance of the fine particle film is 5.8 × 1.
It was 0 4 Ω / □.
【0099】実施例13 実施例11において、空気中での加熱処理時に、図1に
示した温度プロファイル中、300℃での加熱処理に続
いて330℃の空気中に20分放置した以外は、実施例
11と同様にして微粒子膜を作製した。 Example 13 In Example 11, except that during the heat treatment in air, the temperature profile shown in FIG. 1 was followed by a heat treatment at 300 ° C. and then standing in air at 330 ° C. for 20 minutes. A fine particle film was prepared in the same manner as in Example 11.
【0100】実施例11と同様にして、微粒子膜の膜厚
及び形状を測定したところ、実施例11とほぼ同様であ
った。When the thickness and shape of the fine particle film were measured in the same manner as in Example 11, it was almost the same as in Example 11.
【0101】また、微粒子膜のシート抵抗は3.4×1
04 Ω/□であった。The sheet resistance of the fine particle film is 3.4 × 1.
It was 0 4 Ω / □.
【0102】比較例6 実施例11において、空気中での加熱処理を、図1に示
した温度プロファイル中、有機パラジウムの分解温度
(220℃)以上での保持温度を300℃にかえて40
0℃で行った以外は、実施例11と同様にして微粒子膜
を作製した。 Comparative Example 6 In Example 11, the heat treatment in air was carried out in the temperature profile shown in FIG. 1 by changing the holding temperature at the decomposition temperature of the organopalladium (220 ° C.) or higher to 300 ° C.
A fine particle film was produced in the same manner as in Example 11 except that the operation was performed at 0 ° C.
【0103】実施例11と同様にして、微粒子膜の膜厚
及び形状を測定したところ、図22に示すような結果が
得られた。同図においてスキャン幅37μm以降が微粒
子膜部分を示している。When the thickness and shape of the fine particle film were measured in the same manner as in Example 11, the results shown in FIG. 22 were obtained. In the same figure, the scan width of 37 μm or later indicates the fine particle film portion.
【0104】また、微粒子膜のシート抵抗は9.5×1
04 Ω/□であった。The sheet resistance of the fine particle film is 9.5 × 1.
It was 0 4 Ω / □.
【0105】実施例11〜13,比較例6の結果から、
有機パラジウムの熱処理において、分解温度以上での分
解処理時の温度が、これにより形成される微粒子膜の均
一性に大きく影響しているのがわかる。From the results of Examples 11 to 13 and Comparative Example 6,
It can be seen that in the heat treatment of the organopalladium, the temperature during the decomposition treatment above the decomposition temperature greatly affects the uniformity of the fine particle film formed thereby.
【0106】実施例14 本実施例の微粒子膜は次の方法で作製された。 実施例11のにおいて合成した[Pd(OAc)
2 ]6 H2 Oの母液を濃縮して、黄色の細かい針状結晶
[Pd(OAc)2 ]3 ・CH2 Cl2 を得た。DTA
より分解温度を測定したところ205℃であった。 で得た微結晶を実施例11のと同じ方法で処理
し、有機パラジウム溶液を作製した。 実施例11のと同じ方法で上記有機パラジウム溶
液を基体上に塗布後、図1に示した温度プロファイルで
空気中で加熱処理をして微粒子膜を形成した。 Example 14 The fine particle film of this example was prepared by the following method. Synthesized in Example 11 [Pd (OAc)
The mother liquor of 2 ] 6 H 2 O was concentrated to obtain fine yellow needle-like crystals [Pd (OAc) 2 ] 3 .CH 2 Cl 2 . DTA
The decomposition temperature was measured to be 205 ° C. The microcrystals obtained in 1. were treated in the same manner as in Example 11 to prepare an organic palladium solution. After coating the above-mentioned organopalladium solution on the substrate by the same method as in Example 11, heat treatment was performed in the air in the temperature profile shown in FIG. 1 to form a fine particle film.
【0107】上記作製手順で作製した微粒子膜の膜厚及
び形状は、実施例11とほぼ同様、図21に示したよう
な結果となり、シート抵抗は5.4×104 Ω/□であ
った。The film thickness and shape of the fine particle film produced by the above-described production procedure were as shown in FIG. 21, almost the same as in Example 11, and the sheet resistance was 5.4 × 10 4 Ω / □. .
【0108】また、上記有機パラジウム塗布後、実施例
12と同様に加熱処理したものの結果も同様であった。The results of the same heat treatment as in Example 12 after applying the above organic palladium were also the same.
【0109】比較例7 実施例14において、空気中での加熱処理を、図1に示
した温度プロファイル中、有機パラジウムの分解温度
(205℃)以上での保持温度を300℃にかえて40
0℃で行った以外は、実施例14と同様にして微粒子膜
を作製した。 Comparative Example 7 In Example 14, the heat treatment in air was carried out in the temperature profile shown in FIG. 1 by changing the holding temperature at the decomposition temperature (205 ° C.) or higher of the organopalladium to 300 ° C.
A fine particle film was produced in the same manner as in Example 14 except that the operation was performed at 0 ° C.
【0110】この様にして作製した微粒子膜の膜厚及び
形状を測定したところ、比較例6と同様、図22に示し
たような結果となった。When the thickness and shape of the fine particle film thus produced were measured, the results shown in FIG. 22 were obtained as in Comparative Example 6.
【0111】また、微粒子膜のシート抵抗は4×105
Ω/□であった。The sheet resistance of the fine particle film is 4 × 10 5.
It was Ω / □.
【0112】実施例15 本実施例の微粒子膜は次の方法で作製された。 市販の有機パラジウム−酢酸n−ブチル溶液(奥野
製薬工業(株)製CCP−4230)を絶縁性基体上に
スピナー塗布した。尚、上記有機パラジウム溶液の分解
温度は約230℃である。 上記基体を図1に示した温度プロファイルで空気中
で加熱処理して微粒子膜を形成した。 Example 15 The fine particle film of this example was prepared by the following method. A commercially available organic palladium-n-butyl acetate solution (CCP-4230 manufactured by Okuno Chemical Industries Co., Ltd.) was spinner-coated on the insulating substrate. The decomposition temperature of the organic palladium solution is about 230 ° C. The above substrate was heat-treated in air according to the temperature profile shown in FIG. 1 to form a fine particle film.
【0113】上記作製手順で作製した微粒子膜の膜厚及
び形状は、実施例11とほぼ同様、図21に示したよう
な結果となり、シート抵抗は5.0〜6.0×104 Ω
/□の範囲であった。The film thickness and shape of the fine particle film produced by the above-mentioned production procedure were as shown in FIG. 21, almost the same as in Example 11, and the sheet resistance was 5.0 to 6.0 × 10 4 Ω.
The range was / □.
【0114】また、上記有機パラジウム塗布後、実施例
12と同様に加熱処理したものの結果も同様であった。[0114] Further, the results of the same heat treatment as in Example 12 after applying the above organic palladium were the same.
【0115】比較例8 実施例15において、空気中での加熱処理を、図1に示
した温度プロファイル中、有機パラジウムの分解温度
(約230℃)以上での保持温度を300℃にかえて4
00℃で行った以外は実施例15と同様にして微粒子膜
を作製した。 Comparative Example 8 In Example 15, the heat treatment in air was carried out in the temperature profile shown in FIG. 1 by changing the holding temperature at the decomposition temperature of the organopalladium (about 230 ° C.) or higher to 300 ° C.
A fine particle film was prepared in the same manner as in Example 15 except that the operation was carried out at 00 ° C.
【0116】この様にして作製した微粒子膜の膜厚及び
形状を測定したところ、比較例6と同様、図22に示し
たような結果となった。When the thickness and shape of the fine particle film thus produced were measured, the results shown in FIG. 22 were obtained as in Comparative Example 6.
【0117】また、微粒子膜のシート抵抗は3×105
Ω/□であった。The sheet resistance of the fine particle film is 3 × 10 5.
It was Ω / □.
【0118】実施例11〜15,比較例6〜8の他に
も、本発明者らが行った数多くの実験によれば、上記分
解処理時の温度が有機金属の分解温度よりも20℃〜1
00℃高い温度であることが、微粒子膜の均一性にとっ
て非常に好ましいことがわかった。In addition to Examples 11 to 15 and Comparative Examples 6 to 8, according to many experiments conducted by the present inventors, the temperature at the time of the above decomposition treatment was 20 ° C. higher than the decomposition temperature of the organic metal. 1
It has been found that a higher temperature of 00 ° C. is very favorable for the uniformity of the particulate film.
【0119】実施例16 本実施例では、本発明による微粒子膜と基体との密着性
を向上させたものである。 Example 16 In this example, the adhesion between the fine particle film of the present invention and the substrate was improved.
【0120】本実施例の電子放出素子の平面図を図23
(a)に示し、そのA−A’断面図を図23(b)に示
した。同図において、231はソーダライムガラス基
板、232は酸化鉛系低軟化点ガラスコーティング膜、
233及び234は電極、235は微粒子膜を示す。本
実施例の電子放出素子は以下の様に作製された。 ソーダライムガラス基板231上に、絶縁層232
として酸化鉛系低軟化点ガラス膜を約30μmの厚さに
コーティングにより形成した。FIG. 23 is a plan view of the electron-emitting device of this example.
It is shown in (a) and the AA 'cross section figure was shown in FIG.23 (b). In the figure, 231 is a soda lime glass substrate, 232 is a lead oxide-based low softening point glass coating film,
233 and 234 are electrodes, and 235 is a fine particle film. The electron-emitting device of this example was manufactured as follows. Insulating layer 232 on soda lime glass substrate 231
As a lead oxide-based low softening point glass film, a film having a thickness of about 30 μm was formed by coating.
【0121】さらに絶縁層232上に電極233,23
4を形成した。尚、電極の材料としてNi金属を用い
た。電極間隔(図23(a)中のG)は4μmとし、膜
厚は1000Åとした。 次に、所望の位置にスピンナー法により、有機パラ
ジウム(奥野製薬(株)製、CCP−4230)を塗布
した後、図1に示した温度プロファイルで空気中で加熱
処理をして酸化パラジウム(PdO)微粒子(平均粒径
60Å)からなる微粒子膜235を形成した。 続いて、450℃,20分大気焼成を行なって、微
粒子237を絶縁層232の表面に埋め込んだところ、
図23(b)に示す様に、微粒子237は表面に一部を
露呈し、残りの部分が埋まっていた。その後、通電処
理、すなわち電極233及び234の間に電圧を印加し
てフォーミング処理を行なったところ、図23(c)に
示される様に電子放出部236が形成された。Further, electrodes 233, 23 are formed on the insulating layer 232.
4 was formed. In addition, Ni metal was used as the material of the electrode. The electrode interval (G in FIG. 23 (a)) was 4 μm, and the film thickness was 1000 Å. Next, after applying organopalladium (CCP-4230 manufactured by Okuno Chemical Industries Co., Ltd.) at a desired position by a spinner method, heat treatment is performed in the air in the temperature profile shown in FIG. 1 to obtain palladium oxide (PdO). ) A fine particle film 235 made of fine particles (average particle size 60Å) was formed. Subsequently, when the fine particles 237 were embedded in the surface of the insulating layer 232 by performing atmospheric baking at 450 ° C. for 20 minutes,
As shown in FIG. 23B, a part of the fine particles 237 was exposed on the surface and the rest was buried. After that, when an energization process, that is, a forming process by applying a voltage between the electrodes 233 and 234 was performed, an electron emitting portion 236 was formed as shown in FIG. 23C.
【0122】この様にして作成した素子は、微粒子と基
体との密着性が極めて向上しており、1×10-3Paの
真空下において、電極233及び234の間に充分な電
子放出量を得るための電圧を印加したところ、電子放出
部236より放出される電子の変動量が極めて小さくな
ることが確認された。In the device thus produced, the adhesion between the fine particles and the substrate was extremely improved, and a sufficient electron emission amount was obtained between the electrodes 233 and 234 under a vacuum of 1 × 10 −3 Pa. It was confirmed that when the voltage for obtaining was applied, the variation amount of the electrons emitted from the electron emitting portion 236 was extremely small.
【0123】尚、絶縁層232となる低軟化点ガラスか
ら成る膜の成膜方法としては、液体コーティング焼成法
の他にも、印刷焼成法、真空堆積法等を用いることがで
きる。As a method of forming the film made of low softening point glass to be the insulating layer 232, a printing baking method, a vacuum deposition method or the like can be used in addition to the liquid coating baking method.
【0124】また、低軟化点ガラス材料としては、基板
231の材料の歪点温度よりも、その軟化点温度が低
く、かつ基板と熱膨張係数が近似しているものが良い。
一般に酸化鉛系の低軟化点ガラスは軟化点が400℃前
後にあり、熱膨張係数も一般的に使用されているソーダ
ライムガラス基板のそれに近似している。Further, as the low softening point glass material, it is preferable that the softening point temperature thereof is lower than the strain point temperature of the material of the substrate 231, and the thermal expansion coefficient thereof is close to that of the substrate.
Generally, a lead oxide-based low softening point glass has a softening point of around 400 ° C. and a thermal expansion coefficient similar to that of a commonly used soda lime glass substrate.
【0125】[0125]
【発明の効果】以上説明した様に、本発明によれば、有
機金属膜の融点±10℃の温度以上且つ分解温度未満の
温度Taで一定期間、好ましくは1分間以上保持するこ
とにより、基体上に有機金属を一様に展開し、その後、
分解温度以上、好ましくは分解温度よりも20℃〜10
0℃高い温度Tbで熱処理することにより、電子放出膜
(微粒子膜)の膜厚及び形状を均一にできると共に、微
粒子の粒径及び微粒子間隔を電子放出に適した領域に制
御でき、電子放出効率及び電子放出特性に優れた電子放
出膜及び電子放出素子を再現性良く安定して提供するこ
とができる。As explained above, according to the present invention, the substrate is kept at the temperature Ta which is equal to or higher than the melting point of the organometallic film ± 10 ° C. and lower than the decomposition temperature for a certain period, preferably 1 minute or more. Spread the organic metal evenly on top, then
Decomposition temperature or higher, preferably 20 ° C to 10 ° C higher than decomposition temperature
By performing the heat treatment at a temperature Tb higher by 0 ° C., the film thickness and shape of the electron emission film (fine particle film) can be made uniform, and the particle size and particle interval of the particles can be controlled to a region suitable for electron emission, resulting in electron emission efficiency. Further, it is possible to stably provide an electron emitting film and an electron emitting device having excellent electron emitting characteristics with good reproducibility.
【0126】また、上記温度Taまでの昇温速度を1℃
/分以上、更に好ましくは、この昇温速度が、上記温度
Taから上記温度Tbまでの昇温速度以上にすることに
より、より一層均一な素子特性が得られる。Further, the temperature rising rate up to the temperature Ta is 1 ° C.
/ Minute or more, and more preferably, by setting the temperature rising rate to be the temperature rising rate from the temperature Ta to the temperature Tb or more, more uniform element characteristics can be obtained.
【0127】本発明により得られる電子放出素子を電子
線発生装置及び画像形成装置の電子源に適用した場合、
素子間の電子放出部(領域)のばらつきがなくなるた
め、均一な電子放出特性を有する電子線発生装置を得ら
れるばかりでなく、画像形成にあたっても輝度むら、表
示のちらつきの極めて少ない画像を形成することができ
る。When the electron-emitting device obtained by the present invention is applied to an electron beam generator and an electron source of an image forming apparatus,
Since there is no variation in the electron emission portion (region) between the elements, it is possible to obtain not only an electron beam generator having uniform electron emission characteristics, but also to form an image with little unevenness in brightness and flickering in display during image formation. be able to.
【図1】本発明に係る有機金属膜の熱処理に用いた温度
プロファイルの例である。FIG. 1 is an example of a temperature profile used for heat treatment of an organometallic film according to the present invention.
【図2】本発明における電子放出素子の作製工程図の例
である。FIG. 2 is an example of a manufacturing process diagram of an electron-emitting device according to the present invention.
【図3】実施例においてフォーミング処理時に用いた電
圧パルス波形図である。FIG. 3 is a voltage pulse waveform diagram used in the forming process in the example.
【図4】実施例において電子放出素子の電子放出特性の
測定に用いた装置の概略構成図である。FIG. 4 is a schematic configuration diagram of an apparatus used for measuring an electron emission characteristic of an electron emitting element in an example.
【図5】実施例において作製した複数の電子放出素子の
電子放出特性のばらつきを示す図である。FIG. 5 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in Examples.
【図6】比較例において有機金属膜の熱処理に用いた温
度プロファイルである。FIG. 6 is a temperature profile used for heat treatment of an organic metal film in a comparative example.
【図7】比較例において作製した複数の電子放出素子の
電子放出特性のばらつきを示す図である。FIG. 7 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in a comparative example.
【図8】比較例において有機金属膜の熱処理に用いた温
度プロファイルである。FIG. 8 is a temperature profile used for heat treatment of an organic metal film in a comparative example.
【図9】比較例において作製した複数の電子放出素子の
電子放出特性のばらつきを示す図である。FIG. 9 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in a comparative example.
【図10】本発明に係る有機金属膜の熱処理に用いた温
度プロファイルの例である。FIG. 10 is an example of a temperature profile used for heat treatment of the organometallic film according to the present invention.
【図11】実施例において作製した複数の電子放出素子
の電子放出特性のばらつきを示す図である。FIG. 11 is a diagram showing variations in electron emission characteristics of a plurality of electron-emitting devices manufactured in Examples.
【図12】本発明に係る有機金属膜の熱処理に用いた温
度プロファイルの例である。FIG. 12 is an example of a temperature profile used for heat treatment of the organometallic film according to the present invention.
【図13】実施例においてパターン状酸化パラジウム微
粒子膜を作製した際の作製工程図である。FIG. 13 is a manufacturing process diagram when a patterned palladium oxide fine particle film is manufactured in an example.
【図14】実施例において作製したパターン状酸化パラ
ジウム微粒子膜の形状を触針式膜厚計により測定した結
果を示す図である。FIG. 14 is a view showing the results of measuring the shape of the patterned palladium oxide fine particle film produced in the example with a stylus type film thickness meter.
【図15】実施例及び比較例において作製したパターン
状酸化パラジウム微粒子膜の均一性(うねりの頻度)を
示す図である。FIG. 15 is a diagram showing the uniformity (frequency of waviness) of patterned palladium oxide fine particle films produced in Examples and Comparative Examples.
【図16】実施例8において作製した微粒子膜の、微粒
子径と塗布焼成回数の関係を示す図である。16 is a diagram showing the relationship between the particle size and the number of times of coating and baking of the particle film produced in Example 8. FIG.
【図17】実施例9において作製した電子放出素子の平
面図及び断面図である。17A and 17B are a plan view and a cross-sectional view of an electron-emitting device manufactured in Example 9.
【図18】実施例9において作製した電子放出素子の平
面図及び断面図である。FIG. 18 is a plan view and a cross-sectional view of an electron-emitting device manufactured in Example 9.
【図19】比較例5において作製した電子放出素子の平
面図及び断面図である。FIG. 19 is a plan view and a cross-sectional view of an electron-emitting device manufactured in Comparative example 5.
【図20】実施例11で作製した微粒子膜の断面のSE
M像の模式図である。FIG. 20 is an SE of a cross section of the fine particle film produced in Example 11.
It is a schematic diagram of M image.
【図21】実施例において作製した微粒子膜の形状を触
針式膜厚計により測定した結果を示す図である。FIG. 21 is a diagram showing the results of measuring the shape of the fine particle film produced in the example with a stylus type film thickness meter.
【図22】比較例において作製した微粒子膜の形状を触
針式膜厚計により測定した結果を示す図である。FIG. 22 is a diagram showing a result of measuring the shape of a fine particle film produced in Comparative Example by a stylus type film thickness meter.
【図23】実施例16において作製した電子放出素子の
平面図及び断面図である。23A and 23B are a plan view and a cross-sectional view of an electron-emitting device manufactured in Example 16.
【図24】従来例の電子放出素子を示す概略構成図(平
面図)である。FIG. 24 is a schematic configuration diagram (plan view) showing an electron-emitting device of a conventional example.
【図25】従来例の電子放出素子を示す概略構成図(平
面図)である。FIG. 25 is a schematic configuration diagram (plan view) showing a conventional electron-emitting device.
【図26】従来例の電子放出素子の電流−電圧特性を示
す図である。FIG. 26 is a diagram showing current-voltage characteristics of a conventional electron-emitting device.
【図27】電子放出素子の概略構成図(平面図)であ
る。FIG. 27 is a schematic configuration diagram (plan view) of an electron-emitting device.
【図28】図27のA−A’断面図である。28 is a cross-sectional view taken along the line A-A ′ in FIG. 27.
【図29】図28のB−B’断面図である。29 is a cross-sectional view taken along the line B-B ′ of FIG. 28.
【図30】電子放出素子の電子顕微鏡写真の模写図(平
面図)である。FIG. 30 is a copy (plan view) of an electron micrograph of an electron-emitting device.
【図31】図30の電子放出素子の電子放出領域の拡大
電子顕微鏡写真の模写図(平面図)である。31 is a copy (plan view) of an enlarged electron micrograph of an electron emission region of the electron emission device of FIG. 30. FIG.
21 絶縁性基体 22,23 電極 24 微粒子膜 25 電子放出領域 30 電流計 31 電源 32 電流計 33 電源 34 アノード電極 131 絶縁性基体 132 クロム 132’ クロムマスク 133 酸化パラジウム微粒子 171 絶縁性基体 172,173 電極 174 微粒子膜 175 電子放出領域 201 絶縁性基体 202 PdO微粒子 231 ソーダライムガラス基板 232 酸化鉛系低軟化点ガラス 233,234 電極 235 微粒子膜 236 電子放出領域 237 微粒子 1 基板 2,3 電極 4 電子放出部 5 薄膜 6 微粒子 21 Insulating Substrate 22,23 Electrode 24 Fine Particle Film 25 Electron Emitting Region 30 Ammeter 31 Power Supply 32 Ammeter 33 Power Supply 34 Anode Electrode 131 Insulating Substrate 132 Chromium 132 'Chromium Mask 133 Palladium Oxide Fine Particles 171 Insulating Substrate 172,173 Electrodes 174 Fine Particle Film 175 Electron Emitting Region 201 Insulating Substrate 202 PdO Fine Particle 231 Soda Lime Glass Substrate 232 Lead Oxide Low Softening Point Glass 233, 234 Electrode 235 Fine Particle Film 236 Electron Emitting Region 237 Fine Particle 1 Substrate 2, 3 Electrode 4 Electron Emitting Part 5 Thin film 6 Fine particles
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河手 信一 東京都大田区下丸子3丁目30番2号 キヤ ノン株式会社内 (72)発明者 三道 和宏 東京都大田区下丸子3丁目30番2号 キヤ ノン株式会社内 (72)発明者 野村 一郎 東京都大田区下丸子3丁目30番2号 キヤ ノン株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinichi Kawate 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuhiro Michi 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Ichiro Nomura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.
Claims (8)
ることにより電子放出膜を作製する方法において、上記
熱処理時に上記有機金属の分解温度以上の温度Tbまで
昇温する際、有機金属の融点±10℃の温度以上且つ有
機金属の分解温度未満の温度Taで一定期間保持するこ
とを特徴とする電子放出膜の作製方法。1. A method for producing an electron emission film by heat-treating an organometallic film formed on a substrate, wherein when the temperature is raised to a temperature Tb higher than the decomposition temperature of the organometallic during the heat treatment, the melting point of the organometallic film. A method for producing an electron-emitting film, which is characterized by holding at a temperature Ta which is equal to or higher than ± 10 ° C. and lower than a decomposition temperature of an organic metal for a certain period.
以上であることを特徴とする請求項1記載の電子放出膜
の作製方法。2. The method for producing an electron emission film according to claim 1, wherein the temperature holding period at the temperature Ta is 1 minute or more.
0℃〜100℃高い温度であることを特徴とする請求項
1又は2記載の電子放出膜の作製方法。3. The temperature Tb is 2 above the decomposition temperature.
The method for producing an electron-emitting film according to claim 1 or 2, wherein the temperature is higher by 0 ° C to 100 ° C.
特徴とする請求項1〜3いずれかに記載の電子放出膜の
作製方法。4. The method for producing an electron emission film according to claim 1, wherein the temperature Tb is maintained for a certain period of time.
以上であることを特徴とする請求項4記載の電子放出膜
の作製方法。5. The method for producing an electron emission film according to claim 4, wherein the temperature holding period at the temperature Tb is 1 minute or more.
分以上であることを特徴とする請求項1〜5いずれかに
記載の電子放出膜の作製方法。6. The temperature rising rate up to the temperature Ta is 1 ° C. /
It is more than a minute, The manufacturing method of the electron emission film in any one of Claims 1-5 characterized by the above-mentioned.
Taから前記温度Tbまでの昇温速度以上であることを
特徴とする請求項1〜6いずれかに記載の電子放出膜の
作製方法。7. The electron emission film according to claim 1, wherein the temperature rising rate up to the temperature Ta is equal to or higher than the temperature rising rate from the temperature Ta to the temperature Tb. Method.
熱処理することにより電子放出素子を作製する方法にお
いて、電子放出膜を作製する際に、請求項1〜7いずれ
かに記載の方法を用いることを特徴とする電子放出素子
の作製方法。8. A method for producing an electron-emitting device by heat-treating an organometallic film formed between electrodes on a substrate, wherein the method for producing an electron-emitting film according to claim 1. A method for manufacturing an electron-emitting device, characterized by using.
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JP3736293A JP2946153B2 (en) | 1993-02-03 | 1993-02-03 | Method for manufacturing electron-emitting film and electron-emitting device |
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JP3736293A JP2946153B2 (en) | 1993-02-03 | 1993-02-03 | Method for manufacturing electron-emitting film and electron-emitting device |
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JPH06231678A true JPH06231678A (en) | 1994-08-19 |
JP2946153B2 JP2946153B2 (en) | 1999-09-06 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5605483A (en) * | 1993-12-14 | 1997-02-25 | Canon Kabushiki Kaisha | Electron source and production thereof, and image-forming apparatus and production thereof |
US5759080A (en) * | 1987-07-15 | 1998-06-02 | Canon Kabushiki Kaisha | Display device with electron-emitting device with electron-emitting region insulated form electrodes |
US5853310A (en) * | 1994-11-29 | 1998-12-29 | Canon Kabushiki Kaisha | Method of manufacturing electron-emitting device, electron source and image-forming apparatus |
USRE40062E1 (en) * | 1987-07-15 | 2008-02-12 | Canon Kabushiki Kaisha | Display device with electron-emitting device with electron-emitting region insulated from electrodes |
JP2009120866A (en) * | 2007-11-12 | 2009-06-04 | Shin Etsu Chem Co Ltd | Method for depositing rare earth oxide coating film |
WO2010002610A3 (en) * | 2008-06-30 | 2010-04-01 | Varian Medical Systems, Inc. | Thermionic emitter designed to control electron beam current profile in two dimensions |
-
1993
- 1993-02-03 JP JP3736293A patent/JP2946153B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5759080A (en) * | 1987-07-15 | 1998-06-02 | Canon Kabushiki Kaisha | Display device with electron-emitting device with electron-emitting region insulated form electrodes |
USRE40062E1 (en) * | 1987-07-15 | 2008-02-12 | Canon Kabushiki Kaisha | Display device with electron-emitting device with electron-emitting region insulated from electrodes |
US5605483A (en) * | 1993-12-14 | 1997-02-25 | Canon Kabushiki Kaisha | Electron source and production thereof, and image-forming apparatus and production thereof |
US5853310A (en) * | 1994-11-29 | 1998-12-29 | Canon Kabushiki Kaisha | Method of manufacturing electron-emitting device, electron source and image-forming apparatus |
JP2009120866A (en) * | 2007-11-12 | 2009-06-04 | Shin Etsu Chem Co Ltd | Method for depositing rare earth oxide coating film |
WO2010002610A3 (en) * | 2008-06-30 | 2010-04-01 | Varian Medical Systems, Inc. | Thermionic emitter designed to control electron beam current profile in two dimensions |
US7924983B2 (en) | 2008-06-30 | 2011-04-12 | Varian Medical Systems, Inc. | Thermionic emitter designed to control electron beam current profile in two dimensions |
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