JPH03163873A - Charge-transfer complex electric element - Google Patents
Charge-transfer complex electric elementInfo
- Publication number
- JPH03163873A JPH03163873A JP2172710A JP17271090A JPH03163873A JP H03163873 A JPH03163873 A JP H03163873A JP 2172710 A JP2172710 A JP 2172710A JP 17271090 A JP17271090 A JP 17271090A JP H03163873 A JPH03163873 A JP H03163873A
- Authority
- JP
- Japan
- Prior art keywords
- resistance state
- voltage
- charge transfer
- transfer complex
- state
- 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.)
- Pending
Links
- 239000010949 copper Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000002441 reversible effect Effects 0.000 abstract description 5
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 17
- 238000010586 diagram Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003685 thermal hair damage Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- JLTPSDHKZGWXTD-UHFFFAOYSA-N 2-[6-(dicyanomethylidene)naphthalen-2-ylidene]propanedinitrile Chemical compound N#CC(C#N)=C1C=CC2=CC(=C(C#N)C#N)C=CC2=C1 JLTPSDHKZGWXTD-UHFFFAOYSA-N 0.000 description 1
- 102100025683 Alkaline phosphatase, tissue-nonspecific isozyme Human genes 0.000 description 1
- 101710161969 Alkaline phosphatase, tissue-nonspecific isozyme Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001655798 Taku Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、スイッチング素子や記憶素子として使用可能
な電荷移動錯体電気素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a charge transfer complex electric element that can be used as a switching element or a memory element.
［従来の技術］
米国特許第４３７１８８３号明細書や特開昭８２−９５
８７８号公報には、電荷移動錯体化合物を用いた電気素
子が開示されている。[Prior art] U.S. Patent No. 4,371,883 and Japanese Patent Application Laid-Open No. 82-95
No. 878 discloses an electric device using a charge transfer complex compound.
３
第４図は、上記公知技術の基本構成を示す断面図である
。電荷移動錯体層１は対向する一対の第１電極２，第２
電極３の間には設けられ、これらの各部材により電気素
子４が構成されている。3 FIG. 4 is a sectional view showing the basic configuration of the above-mentioned known technology. The charge transfer complex layer 1 includes a pair of opposing first electrodes 2 and a second electrode.
An electric element 4 is provided between the electrodes 3, and each of these members constitutes an electric element 4.
前記電気素子４は、例えば次のようにして作製される。The electric element 4 is manufactured, for example, as follows.
ここで、第１電極２としては、ＣｕまたはＡｇなどのド
ナーとなる拐料からなる基板を用いる。まず、基板を、
中性のアクセプタ分子であるＴＣＮＱ （テトラシアノ
キノジメタン）をアセトニトリル（冶媒）中に廂角ｔｔ
．シたｍ ？ｔＪｉ中にｄす。Here, as the first electrode 2, a substrate made of a donor material such as Cu or Ag is used. First, the board
TCNQ (tetracyanoquinodimethane), a neutral acceptor molecule, is dissolved in acetonitrile (hydrogen) at an angle of tt.
．． Shita m? d during tJi.
この結果、酸化還元反応が起こり、アクセプタ分子のイ
オンラシカルと金属塩が形成される。次に、結晶が適当
な厚さ（数μｍ）になるまで戊長じたら、溶液中から基
板を取りだし、真空乾燥により基板から溶媒を除失する
。更に、前記基板にＡｉ＋またはＣｒを蒸着して第２の
電極３を形成し、電気素子を作製する。As a result, a redox reaction occurs, and an ionic radical of the acceptor molecule and a metal salt are formed. Next, when the crystals are elongated to an appropriate thickness (several μm), the substrate is taken out of the solution and the solvent is removed from the substrate by vacuum drying. Furthermore, Ai+ or Cr is deposited on the substrate to form a second electrode 3, and an electric element is manufactured.
第５図は、・前記電気素子に直列抵抗を介して電圧を印
加した場合の電圧一電流特性（Ｖ− Ｉ特性）を示す。FIG. 5 shows voltage-current characteristics (VI characteristics) when a voltage is applied to the electric element via a series resistor.
同図より、印加電圧がしきい値Ｖ，，，に到４ −
達すると、ロードラインＬに沿ってＡ点からＢ点に移行
する（つまり、不連続な変化が生じる）ことが明らかで
ある。この事は、前記電荷移動錯体層３の抵抗値が高抵
抗状態から低抵抗状態に急変することを示している。こ
うした抵抗変化は、電流制御型の負性正抵抗と呼ばれて
いる。From the same figure, it is clear that when the applied voltage reaches the threshold value V, 4 -, it moves from point A to point B along the load line L (that is, a discontinuous change occurs). . This shows that the resistance value of the charge transfer complex layer 3 suddenly changes from a high resistance state to a low resistance state. Such resistance changes are called current-controlled negative positive resistance.
このように、電荷移動錯体層１は双安定性特性を有する
。即ち、電荷移動錯体層１の抵抗値は、しきい値Ｖ７Ｈ
または−ＶＴＲを境として、一方の安定な状態（高抵抗
状態）から他方の安定な状態（低抵抗状態）に移行する
特性を有する。既述した米国特許の発明者らは、上記現
象が生じるのは、下記（１）式の電気化学反応が所定の
電界Ｅのもとで因体結晶中に生じるからである、と指摘
している。Thus, the charge transfer complex layer 1 has bistability properties. That is, the resistance value of the charge transfer complex layer 1 is equal to the threshold value V7H.
Or, it has a characteristic of transitioning from one stable state (high resistance state) to the other stable state (low resistance state) with -VTR as the boundary. The inventors of the above-mentioned US patents point out that the above phenomenon occurs because the electrochemical reaction of formula (1) below occurs in the factor crystal under a predetermined electric field E. There is.
［Ｃｕ ” （ＴＣＮＱ” ） ］ ｎ −＞ ＣＬＩ
， 十［Ｃｕ ．（ＴＣＮＱ７）］，−， 十（ＴＣ
ＱＮ’ ），・・・（１）
上記発明者らは、上記反応により、有機電荷移動錯体層
１中に電気的に中性なＣｕ とＴＣＮＱ’５
とか等量ずつ生じて電荷移動錯体層３中の導電性を上昇
させ、これにより高抵抗状態から低抵抗状態に変化する
、と指摘している。[Cu” (TCNQ”)] n -> CLI
, ten [Cu. (TCNQ7)], −, ten (TC
QN'),...(1) The above inventors have discovered that the above reaction produces equal amounts of electrically neutral Cu and TCNQ'5 in the organic charge transfer complex layer 1, and the charge transfer complex layer 3 They point out that this increases the conductivity of the material, thereby changing from a high-resistance state to a low-resistance state.
また、上記発明者らは、電荷移動錯体層１が、スイッチ
ング特性Ａを示すか、メモリ特性Ｂを示すかは、錯体を
構成しているアクセプタ分子の酸化還元電位による、と
指摘している。Furthermore, the inventors point out that whether the charge transfer complex layer 1 exhibits the switching characteristic A or the memory characteristic B depends on the redox potential of the acceptor molecules constituting the complex.
スイッチング特性Ａ；印加電圧かしきい値電圧に到達す
ると、高抵抗状態から低抵抗状態に変化し、印加電圧を
除去して零電圧にすると低抵抗状態から高抵抗状態に復
帰する特性。Switching characteristic A: A characteristic that changes from a high resistance state to a low resistance state when the applied voltage reaches a threshold voltage, and returns from the low resistance state to the high resistance state when the applied voltage is removed and the voltage becomes zero.
メモリ特性Ｂ；印加電圧かしきい値に到達して低抵抗状
態に変化すると、印加電圧を除去してもそのまま低抵抗
状態を保持・記憶する特性。Memory characteristic B: When the applied voltage reaches a threshold value and changes to a low resistance state, the low resistance state is maintained and stored even after the applied voltage is removed.
つまり、酸化還元電位の低いアクセプタ分子であるＴ
Ｃ Ｎ Ｑ Ｍ ｅ ２ （２．５−ジメチル−７．
７，８，８．テトラシアノキノジメタン） 、ＴＣＮＱ
（ＯＭｅ）２（ ２．５ ＝ジメルエーテル−７．７
，８，８テトラシアノキノジメタン）などを用いた場合
、スイッチング特性を有する電気素子となる。また、酸
化還元電位の６
高いアクセプタ分子であるＴＣＮＱＦ４ （２，３，
５，６，テ１・ラジルオロ−７．７，８，８，テ１・ラ
シアノキノジメタン）を用いた場合、メモリ特性を有す
る電気素子となる。更に、中間的な酸化還元電位を有す
るＴＣＮＱやＴＮＡＰ （テトラシアノナフ１・キノジ
メタン）を用いた場合、スイッチング特性またはメモリ
特性のいずれかを示す電気素子となる。In other words, T is an acceptor molecule with a low redox potential.
C N Q M e 2 (2.5-dimethyl-7.
7, 8, 8. tetracyanoquinodimethane), TCNQ
(OMe)2(2.5 = dimel ether-7.7
, 8,8 tetracyanoquinodimethane), etc., it becomes an electric element with switching characteristics. In addition, TCNQF4 (2,3,
When 5,6,Te1・radiolo-7.7,8,8,Te1・Racyanoquinodimethane) is used, an electric element having memory properties is obtained. Furthermore, when TCNQ or TNAP (tetracyanonaf-1-quinodimethane), which has an intermediate redox potential, is used, the electric element exhibits either switching characteristics or memory characteristics.
このように、電荷移動錯体電気素子は、電流制御型の負
性抵抗を示す電気素子として注目されている。As described above, charge transfer complex electric devices are attracting attention as electric devices that exhibit negative resistance under current control.
［発明が解決しようとする課題］
しかし、従来の電気素子は、印加電圧がしきい値に到達
すると、高抵抗状態から低抵抗状態に変化する電流制御
型の負性抵抗を示す。このため、第５図のＡ点からＢ点
への移行によって示されているように、低抵抗状態に変
化した際に電流が急激に増大し、電気素子が熱損傷を受
ける恐れがある。熱損傷を受けると、例えばスイッチン
グ特性をもたせた電気素子の場合、印加電圧を除去した
りあるいは印加電圧と逆極性の電流パルスをくわえる等
の消去操作を行なっても、低抵抗状８態から高抵抗状態
に復帰しなくなる。このように、従来の電気素子は、リ
バーシブルなスイッチング動作を安定に行うことができ
ないという問題点を有していた。[Problems to be Solved by the Invention] However, conventional electric elements exhibit current-controlled negative resistance that changes from a high resistance state to a low resistance state when the applied voltage reaches a threshold value. Therefore, as shown by the transition from point A to point B in FIG. 5, when the resistance changes to a low resistance state, the current increases rapidly, and there is a risk that the electric element may be thermally damaged. When thermally damaged, for example, in the case of an electrical element with switching characteristics, even if an erase operation such as removing the applied voltage or adding a current pulse of the opposite polarity to the applied voltage is performed, the resistance state changes from the low resistance state to the high state. It will not return to the resistance state. As described above, conventional electric elements have had the problem of not being able to stably perform reversible switching operations.
本発明は、印加電圧の制御により、ＯＮ状態（記憶状態
）とＯＦＦ状態（消去状態）との二状態（二値）の間を
、安定かつリバーシブルに変化できる電荷移動錯体電気
素子を提供することを目的とする。The present invention provides a charge transfer complex electrical element that can stably and reversibly change between two states (binary values), an ON state (memory state) and an OFF state (erase state), by controlling applied voltage. With the goal.
［課題を解決するための手段と作用コ
本願第１の発明は、対向する一対の電極間に電荷移動錯
体層を有した電気素子において、電極間に印加される第
１電圧が第１のしきい値を越えると電気抵抗が相対的に
高抵抗状態から低抵抗状態に変化し、この後前記第１電
圧と逆極性の第２電圧を電極間に印加して第２のしきい
値を越えると電気抵抗が低抵抗状態から高抵抗状態に変
化することを特徴とする電荷移動錯体電気素子である。[Means and effects for solving the problem] The first invention of the present application is an electric element having a charge transfer complex layer between a pair of opposing electrodes, in which a first voltage applied between the electrodes is a first voltage. When the threshold value is exceeded, the electrical resistance changes from a relatively high resistance state to a low resistance state, and then a second voltage having a polarity opposite to the first voltage is applied between the electrodes to exceed the second threshold value. This is a charge transfer complex electric element characterized in that the electric resistance changes from a low resistance state to a high resistance state.
本願ｍ ２の発明は、対向する一対の電極間に電７，Ｉ
Ｉ移動錯体層を有した電気素子において、電極間に印加
される第１電圧が第１のしきい値を越えると電気抵抗が
相対的に高抵抗状態から低抵抗状態に変化し、この後前
記第１電圧と逆極性の第２電圧を電極間に印加して第２
のしきい値を越えると電気抵抗が低抵抗状態から相対的
に高抵抗状態に変化するとともに、印加電圧が前記第２
のしきい値より大きい第３のしきい値を越えると前記高
低抗状態から前記低抵抗状態より更に低い低抵抗状態に
不可逆的に変化することを特徴とする電荷移動錯体電気
素子である。The invention of m2 of the present application provides an electric current 7, I between a pair of opposing electrodes.
In an electric element having an I-transfer complex layer, when the first voltage applied between the electrodes exceeds the first threshold, the electrical resistance changes from a relatively high resistance state to a relatively low resistance state, and then the above-mentioned A second voltage of opposite polarity to the first voltage is applied between the electrodes to generate a second voltage.
When the threshold value is exceeded, the electrical resistance changes from a low resistance state to a relatively high resistance state, and the applied voltage
The charge transfer complex electric element is characterized in that when a third threshold value, which is larger than the threshold value of , is exceeded, the high-low resistance state irreversibly changes to a low-resistance state that is even lower than the low-resistance state.
本発明に係る電荷移動錯体電気素子は、一対の電極（夫
々銅電極，アルミニウム電極からなり、かつ電荷移動錯
体層が銅−ＴＣＮＱからなることが最も望ましい。更に
、前記銅−ＴＣＮＱは、アセトンとアセトニトリルの混
合溶媒を用いたＴＣＮＱ溶液に銅電極を接触させること
により形成されることがもっとも望ましい。The charge transfer complex electric device according to the present invention has a pair of electrodes (each consisting of a copper electrode and an aluminum electrode, and the charge transfer complex layer is most preferably made of copper-TCNQ. Most preferably, it is formed by contacting a copper electrode with a TCNQ solution using a mixed solvent of acetonitrile.
本発明において、銅一ＴＣＮＱのスイッチングメカニズ
ムについては十分解明されていないが、９
負の電圧でスイッチングするのは次のような理由と推測
される。つまり、
−■
Ｃｕ” ＴＣＮＱ− Ｃｕ” ＋ＴＣＮＱ”の
ようなイオン性結晶中に中性のＣｕ” とＴＣＮＱ゜が
できて抵抗値が下がるものと考えられる。In the present invention, although the switching mechanism of copper-TCNQ has not been fully elucidated, it is presumed that the reason for switching at a negative voltage is as follows. In other words, it is considered that neutral Cu'' and TCNQ° are formed in the ionic crystal such as -■Cu'' TCNQ- Cu''+TCNQ'', and the resistance value decreases.
勿論、中性のＣｕ” とＴＣＮＱ’ はイオン性結晶中
にもわずかながら（ｆ−在しているが、スイッチングに
よりさらにこの数か地加するものと考えられる。スイッ
チング速度が高々４００ Ｈ ｚ （２．５ｍｓｅｃ
）なのは、前記Ｃｕ ，ＴＣＮＱ’の動きが極めて遅
いためと考えられる。Of course, neutral Cu'' and TCNQ' exist in small amounts (f-) in the ionic crystal, but it is thought that this number is added due to switching.The switching speed is at most 400 Hz ( 2.5msec
) is considered to be because the movement of Cu and TCNQ' is extremely slow.
本発明において、ＲＡＭ／ＲＯＭの動作について考察す
ると、ＲＡＭ動作（随時書き込み，消去できる）の場合
は、第６図に示ずように■→■一■のループを繰り返す
。この動作はポーラライズドメモリ動作である。ここで
、ＲＯＭタイプの永久書込み型メモリにするには、高抵
抗状態において＋Ｖ側の印加電圧を加え、図のように＋
１２Ｖ〜＋３Ｖ以上にすればよい。これにより、■→■
のルプを描き、ＲＡＭ動作の場合のＯＮ状態におけ１０
る低抵抗より更に低い抵抗状態に不可逆的に至たらしめ
ることかできる。In the present invention, considering the operation of RAM/ROM, in the case of RAM operation (which can be written and erased at any time), a loop of ■→■1■ is repeated as shown in FIG. This operation is a polarized memory operation. To create a ROM type permanent write memory, apply a voltage on the +V side in a high resistance state, as shown in the figure.
The voltage may be set to 12V to +3V or more. As a result, ■→■
It is possible to irreversibly reach a resistance state even lower than the low resistance of 10 in the ON state in the case of RAM operation.
［実施例］ 以下、本発明の一実施例を第１図を参照して説明する。[Example] An embodiment of the present invention will be described below with reference to FIG.
電気素子１１は、対向する一対の第１の電極（下部電極
）１２，第２の電極（上部電極）１３と、これらの電極
間に介在された電荷移動錯体層１４とから構成されてい
る。ここで、前記第１の電極１２は、常温で熱膨脹率が
Ｃｕと同程度の結晶化ガラス基板ｌ５の一方の主面に形
成されている。また、前記第１の電極１２はＣｕ（銅）
からなり、第２の電極１３はｌ （アルミニウム）か
らなる。直流電源１Ｇの電圧は、１ＫΩ程度の直列抵抗
｛７を介して前記電気素子１ｌの両電極１２． １３に
印加される。電流計１８や電圧計１９も前記電気素子の
電極１２． １３に接続されている。The electric element 11 includes a pair of opposing first electrodes (lower electrodes) 12 and second electrodes (upper electrodes) 13, and a charge transfer complex layer 14 interposed between these electrodes. Here, the first electrode 12 is formed on one main surface of a crystallized glass substrate l5 having a coefficient of thermal expansion comparable to that of Cu at room temperature. Further, the first electrode 12 is made of Cu (copper).
The second electrode 13 is made of l (aluminum). The voltage of the DC power supply 1G is applied to both electrodes 12. 13. The ammeter 18 and the voltmeter 19 are also connected to the electrode 12 of the electric element. 13.
こうした構成の電気素子は、次のように製作されている
。An electric element having such a configuration is manufactured as follows.
まず、常温で熱膨脹率がＣｕと同程度の結晶化１１
ガラス基板１５の一方の主面にＣｕを真空蒸着し、第１
の電極ｌ２を形成した。つづいて、前記托１の電地１２
を２．８９６のフフ化水素酸水溶戚によってエッチング
処理し、蒸留水で洗浄した後、Ａｒガスブロアーで乾燥
した。次に、ＴＣＮＱ （東京化成）をアセトン（和光
・特級）とアセトニトリル（和光・特級）とを１，１の
況含した混合溶媒中に冶解させ、ＴＣＮＱ濃度１００ｍ
ｇ／ ５０ ｍｌ）の溶戚を作った。ひきつづき、この
溶液に前記電極Ｉ２を２０℃の温度下で３０秒間浸漬し
、電極１２上にＣｕ−ＴＣＮＱ結品を成長させた。更に
、前記結晶を成長させた裁板を前記溶戚から取り出し、
アセ１・ンで洗浄して未反応のＴＣＮＱを除去した後、
真空乾燥させて電荷移動錯体層１４を形成した。最後に
、前記電荷移動錯体層ｌ４上にＡρを真空蒸着して第２
の電極１３を形成し、電荷移動錯体電気索子１ｌを製作
した。First, Cu is vacuum-deposited on one main surface of a crystallized glass substrate 15 with a coefficient of thermal expansion similar to that of Cu at room temperature.
An electrode l2 was formed. Continuing, the electric ground 12 of the above-mentioned Taku 1
was etched with aqueous hydrofluoric acid of 2.896, washed with distilled water, and then dried with an Ar gas blower. Next, TCNQ (Tokyo Kasei) was dissolved in a mixed solvent containing acetone (Wako, special grade) and acetonitrile (Wako, special grade) in a 1:1 ratio, and the TCNQ concentration was 100 m
g/50 ml) was prepared. Subsequently, the electrode I2 was immersed in this solution at a temperature of 20° C. for 30 seconds to grow a Cu-TCNQ crystal on the electrode 12. Furthermore, the cut board on which the crystals have grown is removed from the melting plate,
After washing with acetic acid to remove unreacted TCNQ,
A charge transfer complex layer 14 was formed by vacuum drying. Finally, Aρ is vacuum deposited on the charge transfer complex layer l4 to form a second layer.
An electrode 13 was formed, and a charge transfer complex electric cable 1l was manufactured.
以上のように作製した電気素子について第１図に示す回
路を用いてＶ−１特性を測定したところ、第２図に示す
Ｖ−１特性図を得た。ここで、ｌｌｌＪ定１ ２
に際しては、電気素子１１の第１の電極ｌ２及び第２の
電極Ｉ３に対して、第１図の破線で示す極性に接続され
た直流電源１６により、第２の電極１３の側が正となる
「正の電圧」を印加した。しかし、電気索Ｔ−１１はス
イッチング動作しなかった。When the V-1 characteristic of the electric element produced as described above was measured using the circuit shown in FIG. 1, the V-1 characteristic diagram shown in FIG. 2 was obtained. Here, when determining lllJ constant 1 2 , the second electrode is connected to the first electrode l2 and the second electrode I3 of the electric element 11 by the DC power supply 16 connected to the polarity shown by the broken line in FIG. A "positive voltage" in which the side numbered 13 was positive was applied. However, electric cable T-11 did not perform a switching operation.
そこで、第１図の実線で示す極性に接続された直流電源
１６により、第２の電極１３の側が負となる「負の電圧
」を印加した。その結果、電気素子１ｌは、負のしきい
値ＶＴＩで初期状態の高抵抗状態から低抵抗状態に変化
した。初期状態の底抗値はＶＶＴＩで５７．５ＫΩであ
った。また、スイッチング後の低抵抗状態の抵抗値は、
２．３ＫΩであった。Therefore, a "negative voltage" was applied so that the second electrode 13 side was negative using the DC power supply 16 connected to the polarity shown by the solid line in FIG. As a result, the electric element 1l changed from the initial high resistance state to the low resistance state at the negative threshold value VTI. The bottom resistance value in the initial state was VVTI of 57.5KΩ. Also, the resistance value in the low resistance state after switching is
It was 2.3KΩ.
この低抵抗状態は、電気素子１１に印加されている電圧
を取り除いても保持されていた。事実、確認の為、再び
電気素子１！に電圧を加えたところ、やはり低抵抗状態
のままであった。This low resistance state was maintained even when the voltage applied to the electric element 11 was removed. In fact, to confirm the fact, electric element 1 again! When a voltage was applied to it, it remained in a low resistance state.
次に、直流電源１６の極性を再び破線の状態にし、第２
の電極１３の側が正となる「正の電圧」を加えた。「正
の電圧」の大きさが正のしきい値Ｖア，に達すると、電
気素子４は初期状態である高抵抗状１ ３
？に復帰した。Next, the polarity of the DC power supply 16 is changed to the broken line again, and the second
A "positive voltage" was applied so that the side of the electrode 13 was positive. When the magnitude of the "positive voltage" reaches the positive threshold value Va, the electric element 4 is in its initial state of high resistance 1 3 ? returned to.
上記実施例の電気素子ｌ１は、印加電圧の制御による書
き込み操作及び消去操作を行うことにより、ＯＮ状態（
記憶状態）とＯＦＦ状態（消去状態）との二状態（二値
）の間を自６ニに変化する。前記電気素子ｌ１における
記憶情報の読出しは、次のように行う。即ち、記憶状態
（低抵抗状態）にある電気素子１ｌに対し、負のしきい
値電圧より絶対値の小さな「負の電圧」を印加して電流
検出を行えばよい。上記のような電圧信号を人力すると
、記憶状態を示す電流が前記電気素子に流れる。従って
、電流を倹出することにより、記悌悄報を読みだすこと
ができる。前記電気索子ｌ１に正の電圧を印加すると、
印加電圧の大きさまたは印加時間により初期状態に戻す
ことができる。The electric element l1 of the above embodiment is turned on (ON state) by performing write and erase operations by controlling the applied voltage.
It changes between two states (binary values): memory state) and OFF state (erased state). Reading of the stored information in the electric element l1 is performed as follows. That is, current detection may be performed by applying a "negative voltage" whose absolute value is smaller than the negative threshold voltage to the electric element 1l in the memory state (low resistance state). When a voltage signal such as the one described above is applied manually, a current indicating a memory state flows through the electric element. Therefore, by discharging the current, the recorded information can be read out. When a positive voltage is applied to the electric cord l1,
It is possible to return to the initial state by changing the magnitude of the applied voltage or the application time.
第３図は、上述した状態を示すＶ−１特性図である。負
の電圧Ｖ＋ （Ｖｌ ＜ＶＴＩ）を印加した後暫くそ
のままの状態に放置すると、Ｖ−１特性曲線が破線で示
すように低抵抗側に変化する。逆に正の電圧Ｖ２ （Ｖ
２くＶＴ■）を印加した後暫くそ１ ４
のままの状態に放置すると、■−■特性曲線が一点鎖線
で示すように高抵抗側に変化する。また、スイッチング
後の状態Ａを負の電圧Ｖｌｌで読み込むと、状態Ａから
状態Ｂへ移ることになり、メモリの保持時間を長持ちさ
せることが可能となる。FIG. 3 is a V-1 characteristic diagram showing the above-mentioned state. If the negative voltage V+ (Vl<VTI) is left as it is for a while after being applied, the V-1 characteristic curve changes to the low resistance side as shown by the broken line. On the contrary, positive voltage V2 (V
If the voltage is left in the state of 14 for a while after applying VT2), the characteristic curve 2--2 changes to the high resistance side as shown by the dashed line. Furthermore, when the state A after switching is read with a negative voltage Vll, the state A is transferred to the state B, which makes it possible to extend the memory retention time.
上述したように、上記実施例による電気素子Ｉ１は、対
向する第１の電極１２と第２の電極１３との間に印加し
た負の電圧値が負のしきい値に到達すると、抵抗状態は
初期状態の相対的に高抵抗な状態から低抵抗な状態に変
化する。ひきつづき、第１の電極１２と第２の電極ｌ３
との間に印加した正の電圧値が正のしきい値に到達する
と、抵抗状態は相対的に低抵抗な状態から尚抵抗な状態
に表化し、元の状態に１ｋ帰する。このように、本発明
は、印加電圧の極性に対して方向性を有する（リバーシ
ブルなスイッチング特性を有する）点に特徴がある。As described above, in the electric element I1 according to the above embodiment, when the negative voltage value applied between the opposing first electrode 12 and second electrode 13 reaches a negative threshold value, the resistance state changes. The initial state of relatively high resistance changes to a state of low resistance. Continuing, the first electrode 12 and the second electrode l3
When the positive voltage value applied between reaches a positive threshold value, the resistance state changes from a relatively low resistance state to a still high resistance state and returns to the original state by 1k. As described above, the present invention is characterized in that it has directionality (has reversible switching characteristics) with respect to the polarity of the applied voltage.
なお、上記実施例においても、高抵抗状態から低抵抗状
態に移行する場合、電流増大によって熱損傷が生じると
いう問題は本質的にはなくならな１５
い。しかし、スイッチング後、一定電圧が印加されてい
る間は一定電流しか流れない。従って、第１図に示した
ように、例えば１ＫΩ程度の直列抵抗ｌ７を介して電圧
印加を行えば、過大な電流が流れることはなく、熱損傷
の問題は実質的に解決できる。かくして、常に良奸な繰
り返し特性が得られる。Note that even in the above embodiments, the problem of thermal damage occurring due to an increase in current cannot be essentially eliminated when transitioning from a high resistance state to a low resistance state. However, after switching, only a constant current flows while a constant voltage is applied. Therefore, as shown in FIG. 1, if a voltage is applied via a series resistor l7 of, for example, about 1 KΩ, an excessive current will not flow, and the problem of thermal damage can be substantially solved. In this way, good repeatability is always obtained.
また、上記実施例の電気素子Ｉ１においては、高抵抗状
態から低抵抗状態に移行した後、電荷移動錯体電気素子
１１に印加している電圧を取り去っても、低抵抗状態が
保持される（メモリ特性がある）。このメモリ特性を解
除するには、正の電圧を加えればよい。Further, in the electric element I1 of the above embodiment, even after the voltage applied to the charge transfer complex electric element 11 is removed after the transition from the high resistance state to the low resistance state, the low resistance state is maintained (memory characteristics). This memory characteristic can be canceled by applying a positive voltage.
本発明は上記大施例にｌｉＬＬｌ’Ｍされるものではな
く、本発明の要旨を逸脱しない範囲で抽々変形すること
ができることは勿論のことである。具体的には、下記第
１表のＮｏ．２〜Ｎｏ．ｌ２のようにＴＣＮＱ濃度，ア
セトン濃度比率，温度，浸漬時間をかえて試験したとこ
ろ、上記実施例（Ｎｏ、１）と略同様な効果が得られた
。但し、Ｎｏ．５．１６
Ｎｏ．
１０，
Ｎｏ．
１１，
Ｎｏ．
ｉ２の場合、
面内での
結晶の均一性は良くないが、
ＳＷ特性はある。It goes without saying that the present invention is not limited to the above-mentioned embodiments, and can be modified at will without departing from the gist of the present invention. Specifically, No. 1 in Table 1 below. 2~No. When the test was conducted by changing the TCNQ concentration, acetone concentration ratio, temperature, and immersion time as in 12, substantially the same effect as in the above Example (No. 1) was obtained. However, No. 5.16 No. 10, No. 11, No. In the case of i2, the in-plane crystal uniformity is not good, but it has SW characteristics.
但し、 アセトン濃度比率は １ ７ また、Ｃｕ基板処理は全て２．８％ＨＦ酸を用いた。however, The acetone concentration ratio is 1 7 In addition, 2.8% HF acid was used for all Cu substrate treatments.
［発明の効果］
本発明によれば、印加電圧の制御により、ＯＮ状態（記
憶状態）とＯＦＦ状態（消去状態）との二状態（二値）
の間を、安定かつリバーシブルに変化し、例えばリバー
シブルなスイッチング動作を長期に亙って安定に行い得
る等、高い信頼性をもって作動するスイッチング素子及
びメモリ素子として使用できる電荷移動錯体電気素子を
提供できる。[Effects of the Invention] According to the present invention, two states (binary values), an ON state (memory state) and an OFF state (erased state), are achieved by controlling the applied voltage.
It is possible to provide a charge transfer complex electrical element that can be used as a switching element and a memory element that operates with high reliability, for example, can stably and reversibly change between .
第１図は本発明の一実施例に係る電荷移動錯体電気素子
の構或を示す図、第２図及び第３図は夫々第１図の電気
素子の作用を説明するためのＶＩ特性図、第４図は従来
の電Ｑ移動錯体電気素子の址本構成を示す図、第５図は
第４図の電気素子の作用を説明するためのＶ−１特性図
、第６図はＲ Ａ Ｍ ／ Ｒ Ｏ Ｍの動作を説明す
るためのＶ−■特性図である。
１ ８
１１・・・電気素子、１２・・・第１の電極、１３・・
・第２の電極ｌ３、１４・・・電荷移動錯体層、１５・
・・結晶化ガラス基板、１６・・・直流電源、１７・・
・直列抵抗、１８・・電流計、ｌ９・電圧計。FIG. 1 is a diagram showing the structure of a charge transfer complex electric device according to an embodiment of the present invention, and FIGS. 2 and 3 are VI characteristic diagrams for explaining the action of the electric device shown in FIG. 1, respectively. Fig. 4 is a diagram showing the basic configuration of a conventional electric Q-transfer complex electric element, Fig. 5 is a V-1 characteristic diagram for explaining the action of the electric element shown in Fig. 4, and Fig. 6 is a diagram showing the R A M FIG. 2 is a V-■ characteristic diagram for explaining the operation of ROM. 1 8 11... Electric element, 12... First electrode, 13...
・Second electrode l3, 14...charge transfer complex layer, 15.
...Crystalline glass substrate, 16...DC power supply, 17...
・Series resistance, 18...ammeter, l9・voltmeter.
Claims (1)
気素子において、電極間に印加される第１電圧が第１の
しきい値を越えると電気抵抗が相対的に高抵抗状態から
低抵抗状態に変化し、この後前記第１電圧と逆極性の第
２電圧を電極間に印加して第２のしきい値を越えると電
気抵抗が低抵抗状態から高抵抗状態に変化することを特
徴とする電荷移動錯体電気素子。 ２、前記低抵抗状態で印加電圧を除去しても低抵抗状態
を保持する特性を有する請求項１記載の電荷移動錯体電
気素子。 ３、電極間に第１のしきい値、第２のしきい値を越える
極性の異なる電圧を交互に印加することにより、抵抗状
態が高抵抗状態と低抵抗状態との間で交互に変化する特
性を有する請求項１記載の電荷移動錯体電気素子。 ４、一対の電極が夫々銅電極、アルミニウム電極であり
、電荷移動錯体層が銅−ＴＣＮＱからなる請求項１記載
の電荷移動錯体電気素子。 ５、前記銅−ＴＣＮＱは、アセトンとアセトニトリルの
混合溶媒を用いたＴＣＮＱ溶液に銅電極を接触させるこ
とにより形成される請求項４記載の電荷移動錯体電気素
子。 ６、前記第１のしきい値と第２のしきい値の前後におけ
る抵抗状態の変化を用いて書替え可能な記憶素子として
用いる請求項１記載の電荷移動錯体電気素子。 ７、書替え可能な記憶素子の抵抗状態の検出は、第１の
しきい値より低くかつ該第１のしきい値と同じ極性の電
圧を印加することにより行う請求６記載の電荷移動錯体
電気素子。８、対向する一対の電極間に電荷移動錯体層
を有した電気素子において、電極間に印加される第１電
圧が第１のしきい値を越えると電気抵抗が相対的に高抵
抗状態から低抵抗状態に変化し、この後前記第１電圧と
逆極性の第２電圧を電極間に印加して第２のしきい値を
越えると電気抵抗が低抵抗状態から相対的に高抵抗状態
に変化するとともに、印加電圧が前記第２のしきい値よ
り大きい第３のしきい値を越えると前記高抵抗状態から
前記低抵抗状態より更に低い低抵抗状態に不可逆的に変
化することを特徴とする電荷移動錯体電気素子。 ９、前記第１のしきい値と第２のしきい値の前後におけ
る抵抗状態の変化を用いて書替え可能な記憶素子として
用い、前記第３のしきい値の前後における抵抗状態の変
化を用いて書替え不能な記憶素子として用いる請求項８
記載の電荷移動錯体電気素子。[Claims] 1. In an electric element having a charge transfer complex layer between a pair of opposing electrodes, when the first voltage applied between the electrodes exceeds the first threshold, the electric resistance becomes relatively When the electrical resistance changes from a high resistance state to a low resistance state, and then a second voltage of opposite polarity to the first voltage is applied between the electrodes and exceeds the second threshold, the electrical resistance changes from a low resistance state to a high resistance state. A charge transfer complex electric device characterized by a change in state. 2. The charge transfer complex electric device according to claim 1, which has a characteristic of maintaining the low resistance state even if the applied voltage is removed in the low resistance state. 3. By alternately applying voltages with different polarities exceeding the first threshold value and the second threshold value between the electrodes, the resistance state alternately changes between a high resistance state and a low resistance state. The charge transfer complex electric device according to claim 1, having the following characteristics. 4. The charge transfer complex electric device according to claim 1, wherein the pair of electrodes is a copper electrode and an aluminum electrode, respectively, and the charge transfer complex layer is made of copper-TCNQ. 5. The charge transfer complex electric device according to claim 4, wherein the copper-TCNQ is formed by bringing a copper electrode into contact with a TCNQ solution using a mixed solvent of acetone and acetonitrile. 6. The charge transfer complex electric device according to claim 1, which is used as a rewritable memory element using a change in resistance state before and after the first threshold value and the second threshold value. 7. The charge transfer complex electric element according to claim 6, wherein the resistance state of the rewritable memory element is detected by applying a voltage lower than a first threshold value and having the same polarity as the first threshold value. . 8. In an electric element having a charge transfer complex layer between a pair of opposing electrodes, when the first voltage applied between the electrodes exceeds the first threshold, the electrical resistance changes from a relatively high resistance state to a low resistance state. The electrical resistance changes from a low resistance state to a relatively high resistance state when a second voltage of opposite polarity to the first voltage is applied between the electrodes and the second threshold is exceeded. At the same time, when the applied voltage exceeds a third threshold value that is higher than the second threshold value, the high resistance state irreversibly changes to a low resistance state that is lower than the low resistance state. Charge transfer complex electric device. 9. Used as a rewritable memory element using changes in resistance state before and after the first threshold and the second threshold, and using changes in resistance state before and after the third threshold. Claim 8: Used as a non-rewritable storage element.
The charge transfer complex electrical device described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2172710A JPH03163873A (en) | 1989-08-31 | 1990-07-02 | Charge-transfer complex electric element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22560189 | 1989-08-31 | ||
| JP1-225601 | 1989-08-31 | ||
| JP2172710A JPH03163873A (en) | 1989-08-31 | 1990-07-02 | Charge-transfer complex electric element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03163873A true JPH03163873A (en) | 1991-07-15 |
Family
ID=26494975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2172710A Pending JPH03163873A (en) | 1989-08-31 | 1990-07-02 | Charge-transfer complex electric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03163873A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008124360A (en) * | 2006-11-15 | 2008-05-29 | Sony Corp | Functional molecular element, manufacturing method thereof and functional molecular device |
-
1990
- 1990-07-02 JP JP2172710A patent/JPH03163873A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008124360A (en) * | 2006-11-15 | 2008-05-29 | Sony Corp | Functional molecular element, manufacturing method thereof and functional molecular device |
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