JP5881077B2 - Electrode and organic electronic device using the same - Google Patents
Electrode and organic electronic device using the same Download PDFInfo
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 239000002105 nanoparticle Substances 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000010408 film Substances 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Description
本発明は、有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子と略称する）や有機薄膜トランジスタ（以下、有機ＴＦＴと略称する）、有機薄膜太陽電池等の有機電子デバイスの電極材料に関し、特に、銀ナノ粒子を適用した電極及びそれを用いた有機電子デバイスに関する。 The present invention relates to an electrode material for an organic electronic device such as an organic electroluminescence element (hereinafter abbreviated as an organic EL element), an organic thin film transistor (hereinafter abbreviated as an organic TFT), an organic thin film solar cell, etc. And an organic electronic device using the same.
有機電子デバイスにおいては、デバイス効率の向上のため、活性層における有機半導体やその他の層を構成する有機材料のみならず、各金属電極材料の選択も重要である。
例えば、有機ＴＦＴでは、Ｐ型有機ＴＦＴにおいては、ソース電極から有機半導体のＨＯＭＯ準位に電荷が注入されるため、有機半導体への電荷注入障壁を小さくする観点から、ソース電極・ドレイン電極には仕事関数の大きい金属が用いられる。一般的には、Ａｕ等の仕事関数が４．８〜５．０ｅＶ程度の金属が用いられている。
一方、Ｎ型ＴＦＴにおいては、ソース電極から有機半導体のＬＵＭＯ準位に電荷が注入されるため、有機半導体への電荷注入障壁を小さくする観点から、ソース電極・ドレイン電極には仕事関数の小さい金属が用いられる。一般的には、Ａｌ等の仕事関数が４．２〜４．５ｅＶ程度の金属が用いられている。
In an organic electronic device, in order to improve device efficiency, it is important to select each metal electrode material as well as an organic semiconductor constituting the active layer and other layers in the active layer.
For example, in an organic TFT, in a P-type organic TFT, charges are injected from the source electrode to the HOMO level of the organic semiconductor. From the viewpoint of reducing the charge injection barrier to the organic semiconductor, A metal having a high work function is used. In general, a metal having a work function of about 4.8 to 5.0 eV such as Au is used.
On the other hand, in the N-type TFT, since a charge is injected from the source electrode to the LUMO level of the organic semiconductor, a metal having a low work function is used for the source electrode and the drain electrode from the viewpoint of reducing the charge injection barrier to the organic semiconductor. Is used. In general, a metal having a work function of about 4.2 to 4.5 eV such as Al is used.
このように、電荷注入障壁を小さくし、電極の接触抵抗を低減させるためには、仕事関数に応じて電極材料を使い分ける必要があった。 Thus, in order to reduce the charge injection barrier and reduce the contact resistance of the electrode, it is necessary to use different electrode materials depending on the work function.
ところで、新たな導電性塗布膜形成材料として、複合金属超微粒子の開発が進められており、例えば、特許文献１には、安定で取り扱いが容易であり、導電膜の形成性に優れたものとして、粒子径がｎｍレベルの銀超微粒子、いわゆる銀ナノ粒子が、本出願人によって提案されている。 By the way, development of composite metal ultrafine particles has been advanced as a new conductive coating film forming material. For example, in Patent Document 1, it is stable and easy to handle, and has excellent formability of a conductive film. The present applicant has proposed silver ultrafine particles having a particle size of the nm level, so-called silver nanoparticles.
本発明者らは、有機電子デバイスの電極材料として、塗布成膜が可能である前記銀ナノ粒子に着目して検討した結果、この銀ナノ粒子は、仕事関数を制御することが可能であることを見出した。
これに基づいて、本発明は、有機電子デバイスにおいて、仕事関数を制御することにより、電極から有機半導体への電荷注入障壁をより小さくすることが可能となる銀ナノ粒子を適用した電極及びそれを用いた有機電子デバイスを提供することを目的とするものである。
As a result of examining the silver nanoparticles that can be applied and formed as an electrode material of an organic electronic device, the present inventors have found that the silver nanoparticles can control the work function. I found.
Based on this, the present invention relates to an electrode to which silver nanoparticles are applied, which makes it possible to further reduce the charge injection barrier from the electrode to the organic semiconductor by controlling the work function in the organic electronic device, and It aims at providing the used organic electronic device.
本発明に係る有機電子デバイスの製造方法は、平均粒径が３０ｎｍ以下であり、沸点が１００〜２５０℃の範囲内にあるアルキルアミンと沸点が１００〜２５０℃の範囲内にあるアルキルジアミンを主成分とする保護分子により覆われた銀ナノ粒子を電極として塗布する工程と、当該塗布された銀ナノ粒子の電極を仕事関数に応じた温度で焼成することにより、前記仕事関数を有する銀ナノ粒子の電極を形成する工程とを有することを特徴とする。
前記仕事関数は４．２５〜４．８５ｅＶであることが好ましい。
有機電子デバイスの電極材料として、このような銀ナノ粒子を適用することにより、仕事関数の制御が可能となり、電極から有機半導体への電荷注入障壁をより小さくすることができる。
Method for producing an organic electronic device according to the present invention, the average particle size is at 30nm or less, the near boiling point is near Rua Rukiruamin and boiling in the range of 100 to 250 ° C. in the range of 100 to 250 ° C. Rua Rukirujiamin The silver having the work function is obtained by applying, as an electrode, silver nanoparticles covered with a protective molecule containing as a main component, and firing the electrode of the applied silver nanoparticles at a temperature corresponding to the work function. Forming a nanoparticle electrode .
The work function is preferably 4.25 to 4.85 eV.
By applying such silver nanoparticles as an electrode material of an organic electronic device, the work function can be controlled, and the charge injection barrier from the electrode to the organic semiconductor can be further reduced.
本発明に係る有機電子デバイスは、少なくとも１つの電極を用いてなる有機電子デバイスであって、前記少なくとも１つの電極が、平均粒径が３０ｎｍ以下であり、沸点が１００〜２５０℃の範囲内にあるアルキルアミンと沸点が１００〜２５０℃の範囲内にあるアルキルジアミンを主成分とする保護分子により覆われた銀ナノ粒子を電極として塗布する工程と、当該塗布された銀ナノ粒子の電極を仕事関数に応じた温度で焼成することにより、前記仕事関数を有する銀ナノ粒子の電極を形成する工程とにより形成されたものであることを特徴とする。 The organic electronic device according to the present invention is an organic electronic device using at least one electrode, and the at least one electrode has an average particle size of 30 nm or less and a boiling point in a range of 100 to 250 ° C. a step of Ah luer Rukiruamin and boiling is applied as an electrode of silver nanoparticles covered by a protective molecules composed mainly of the near-luer Rukirujiamin range of 100 to 250 ° C., the electrodes of the coated silver nanoparticles the by firing at a temperature corresponding to the work function, characterized in der Rukoto those formed by forming an electrode of silver nanoparticles having a work function.
前記仕事関数は４．２５〜４．８５ｅＶであることが好ましい。
前記電極はソース電極、ゲート電極及びドレイン電極からなる群より選択される少なくとも一つの電極であり、選択された電極のうち、少なくとも一つの電極は他の電極とは仕事関数が異なることが好ましい。
前記電極はいずれも前記銀ナノ粒子からなり、各電極に仕事関数の異なる銀ナノ粒子を用いることもできる。
これにより、１つの有機電子デバイスにおいて、異なる種類の電極材料を使い分ける必要がなく、容易に仕事関数の制御が可能である１種類の材料での各電極の形成が可能となる。
The work function is preferably 4.25 to 4.85 eV.
The electrode is at least one electrode selected from the group consisting of a source electrode, a gate electrode, and a drain electrode, and at least one of the selected electrodes preferably has a work function different from other electrodes .
Each of the electrodes is composed of the silver nanoparticles, and silver nanoparticles having different work functions can be used for each electrode.
Thereby, in one organic electronic device, it is not necessary to use different types of electrode materials, and it is possible to form each electrode with one type of material that can easily control the work function.
また、前記電極のうち、仕事関数のより大きい電極は、１００℃以上１５０℃以下の温度で焼成されたものであることが好ましい。
焼成温度が１００℃付近を境にして、低温と高温とで仕事関数が大きく変化することに基づくものである。
Also, among the pre-Symbol electrodes, larger electrode work function is preferably one which has been calcined at 100 ° C. or higher 0.99 ° C. or lower.
This is based on the fact that the work function varies greatly between the low temperature and the high temperature with the firing temperature around 100 ° C.
本発明に係る電極によれば、有機電子デバイスの電極材料として銀ナノ粒子を用いることにより、仕事関数の制御が可能となり、電極から有機半導体への電荷注入障壁をより小さくすることが可能となる。
さらに、前記銀ナノ粒子は、Ｐ型、Ｎ型のいずれの有機ＴＦＴにも適用し得る電極材料であり、仕事関数の制御によって、動作電圧の低下等のＴＦＴ性能の向上を図ることができる。
したがって、本発明に係る電極を用いることにより、有機ＴＦＴのみならず、有機ＥＬ素子や有機薄膜太陽電池等の様々な有機電子デバイスの効率向上が期待される。
According to the electrode of the present invention, by using silver nanoparticles as an electrode material of an organic electronic device, the work function can be controlled, and the charge injection barrier from the electrode to the organic semiconductor can be further reduced. .
Furthermore, the silver nanoparticles are electrode materials that can be applied to both P-type and N-type organic TFTs, and can improve TFT performance such as reduction in operating voltage by controlling the work function.
Therefore, the use of the electrode according to the present invention is expected to improve the efficiency of not only organic TFTs but also various organic electronic devices such as organic EL elements and organic thin film solar cells.
以下、本発明について、より詳細に説明する。
本発明に係る電極は、銀ナノ粒子を用いた有機電子デバイス用電極である。
本発明でいう有機電子デバイスとは、有機層を含む積層構造を備えた電子デバイスであり、有機ＥＬ素子、有機ＴＦＴ、有機薄膜太陽電池等の総称として用いる。前記有機電子デバイスは、基板上に１対の電極を備え、前記電極間に少なくとも１層の有機層を備えた構造からなる。
Hereinafter, the present invention will be described in more detail.
The electrode according to the present invention is an electrode for an organic electronic device using silver nanoparticles.
The organic electronic device referred to in the present invention is an electronic device having a laminated structure including an organic layer, and is used as a general term for organic EL elements, organic TFTs, organic thin-film solar cells, and the like. The organic electronic device has a structure in which a pair of electrodes is provided on a substrate, and at least one organic layer is provided between the electrodes.
前記銀ナノ粒子は、平均粒径が３０ｎｍ以下であり、沸点が１００〜２５０℃の範囲内にある中短鎖アルキルアミンと沸点が１００〜２５０℃の範囲内にある中短鎖アルキルジアミンを主成分とする保護分子により覆われた超微粒子である。このような銀ナノ粒子は、本願出願人によって提案されたものであり、具体的な構成及び製造方法については、上述した特許文献２（特開２０１０−２６５５４３号公報）に開示されている。
本発明は、前記銀ナノ粒子が、低温で良好な導電性薄膜を形成し得る材料である上に、焼成温度によって仕事関数に大きな差異が生じることを見出したことに基づいてなされたものである。
このような銀ナノ粒子を有機電子デバイスの電極に応用することにより、仕事関数の制御が可能となり、電極から有機半導体への電荷注入障壁をより小さくすることができ、結果的にデバイス効率の向上を図ることができる。
The silver nanoparticles are mainly composed of medium and short chain alkylamines having an average particle size of 30 nm or less and a boiling point in the range of 100 to 250 ° C. and medium and short chain alkyldiamines in the range of 100 to 250 ° C. Ultrafine particles covered with protective molecules as components. Such silver nanoparticles have been proposed by the applicant of the present application, and a specific configuration and manufacturing method are disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 2010-265543) described above.
The present invention has been made based on the finding that the silver nanoparticles are a material capable of forming a good conductive thin film at a low temperature and that there is a large difference in work function depending on the firing temperature. .
By applying such silver nanoparticles to the electrodes of organic electronic devices, it is possible to control the work function and to further reduce the charge injection barrier from the electrodes to the organic semiconductor, resulting in improved device efficiency. Can be achieved.
図１に、前記銀ナノ粒子の焼成温度による仕事関数の変化を表したグラフを示す。これは、下記実施例において製造した銀ナノ粒子の分散液を用いて、ガラス基板上にスピンコートにより塗布膜を形成し、各温度で焼成し、ＡＣ−３（理研計器株式会社）により各塗布膜について測定した仕事関数である。
図１から分かるように、焼成温度１００℃付近を境に、高温になると銀ナノ粒子塗布膜の仕事関数は約０．５ｅＶ上昇する。
In FIG. 1, the graph showing the change of the work function by the calcination temperature of the said silver nanoparticle is shown. This is achieved by forming a coating film on a glass substrate by spin coating using a dispersion of silver nanoparticles produced in the following examples, baking at various temperatures, and applying each coating with AC-3 (RIKEN Keiki Co., Ltd.). It is the work function measured for the membrane.
As can be seen from FIG. 1, the work function of the silver nanoparticle coating film increases by about 0.5 eV at a high temperature around the baking temperature of about 100 ° C.
図２，３に、銀ナノ粒子塗布膜の電子顕微鏡写真を示す。図２は焼成温度８０℃の場合、図３は焼成温度１００℃の場合である。
図２，３の比較から分かるように、焼成温度が８０℃の場合は、ナノ粒子が観察され、焼成温度８０℃以下の場合は、いずれも同様である。一方、焼成温度が１００℃の場合は、ナノ粒子はほとんど見られず、粒子同士が結合した状態となっており、焼成温度が１００℃以上の場合は、いずれも同様である。
このような焼成によって起こる銀ナノ粒子の粒子形態や粒子サイズの変化が、仕事関数の変化に影響を及ぼしていると考えられる。
2 and 3 show electron micrographs of the silver nanoparticle coating film. FIG. 2 shows the case where the firing temperature is 80 ° C., and FIG. 3 shows the case where the firing temperature is 100 ° C.
As can be seen from the comparison between FIGS. 2 and 3, nanoparticles are observed when the firing temperature is 80 ° C., and the same is true when the firing temperature is 80 ° C. or lower. On the other hand, when the firing temperature is 100 ° C., almost no nanoparticles are seen, and the particles are in a bonded state. When the firing temperature is 100 ° C. or higher, both are the same.
It is considered that changes in the particle shape and particle size of the silver nanoparticles caused by such firing affect the change in work function.
したがって、上記のような銀ナノ粒子を用いて塗布膜形成の際の焼成温度を変化させることにより、仕事関数の大小を制御することが可能となる。すなわち、仕事関数の小さい電極を形成する必要がある場合には、１００℃未満の焼成温度で銀ナノ粒子塗布膜を形成し、また、仕事関数の大きい電極を形成する必要がある場合には、１００℃以上の焼成温度で銀ナノ粒子塗布膜を形成すればよい。
このように、仕事関数を容易に制御可能であれば、電極から有機半導体への電荷注入障壁をより小さくすることが可能となり、動作電圧の低減化を図ることができる。
Therefore, it is possible to control the size of the work function by changing the firing temperature when forming the coating film using the silver nanoparticles as described above. That is, when it is necessary to form an electrode with a low work function, a silver nanoparticle coating film is formed at a firing temperature of less than 100 ° C., and when it is necessary to form an electrode with a high work function, What is necessary is just to form a silver nanoparticle coating film at the calcination temperature of 100 degreeC or more.
Thus, if the work function can be easily controlled, the charge injection barrier from the electrode to the organic semiconductor can be further reduced, and the operating voltage can be reduced.
また、前記銀ナノ粒子からなる電極の仕事関数は、焼成による銀ナノ粒子の粒子形態や粒子サイズの変化の影響を受けることから、それらの変化が起こる焼結温度の制御によっても仕事関数を制御することができる。
粒子形態及び粒子サイズが変化する焼結温度は、銀ナノ粒子の保護分子のアルキル鎖長や構造を変化させることで任意に調節可能である。したがって、本願出願人によって提案された銀ナノ粒子の合成法（特開２０１０−２６５５４３号公報）を用いて、保護分子の構造を最適化した銀ナノ粒子を作製し、前記焼結温度を変化させることにより、仕事関数を制御することも可能である。
In addition, the work function of the electrode composed of silver nanoparticles is affected by changes in the particle morphology and particle size of the silver nanoparticles due to firing, so the work function is also controlled by controlling the sintering temperature at which these changes occur. can do.
The sintering temperature at which the particle morphology and particle size change can be arbitrarily adjusted by changing the alkyl chain length and structure of the protective molecules of the silver nanoparticles. Therefore, silver nanoparticles having an optimized protective molecule structure are prepared using the silver nanoparticle synthesis method proposed by the present applicant (Japanese Patent Laid-Open No. 2010-265543), and the sintering temperature is changed. Thus, it is possible to control the work function.
また、上記のような銀ナノ粒子を用いた電極は、材料の利用効率が低く、高コストである真空蒸着等によらずに、有機溶媒分散液の塗布により、大面積かつフレキシブルな成膜が可能である。しかも、銀ナノ粒子塗布膜形成の際の焼成温度が１５０℃以下と低温であるため、有機電子デバイスを構成する有機材料の劣化に対する影響もほとんどなく、有機材料の機能を低下させるおそれもないことから、電極として好適である。 In addition, the electrode using silver nanoparticles as described above is capable of forming a large area and a flexible film by applying an organic solvent dispersion liquid without using high-cost vacuum deposition or the like because of low material utilization efficiency. Is possible. Moreover, since the firing temperature at the time of forming the silver nanoparticle coating film is as low as 150 ° C. or less, there is almost no influence on the deterioration of the organic material constituting the organic electronic device, and there is no possibility of lowering the function of the organic material. Therefore, it is suitable as an electrode.
前記銀ナノ粒子を用いた電極は、有機電子デバイスの電極の１つとして用いてもよく、あるいはまた、上述したように、焼成温度を変化させることにより仕事関数を制御することができるため、１つのデバイスのいずれの電極にも前記銀ナノ粒子を用いることができる。
このように、銀ナノ粒子を電極材料として用いれば、１つの有機電子デバイスにおいて、異なる種類の電極材料を選択して使い分ける必要がなく、容易に仕事関数の制御が可能である１種類の材料により各電極を形成することができる。
また、銀ナノ粒子によれば、Ｐ型又はＮ型のいずれの有機ＴＦＴであっても、１種類の材料によって電極を形成することが可能となり、しかも、各有機ＴＦＴの性能向上を図ることもできる。
The electrode using the silver nanoparticles may be used as one of the electrodes of the organic electronic device. Alternatively, as described above, the work function can be controlled by changing the firing temperature. The silver nanoparticles can be used for any electrode of one device.
As described above, when silver nanoparticles are used as an electrode material, it is not necessary to select and use different types of electrode materials in one organic electronic device, and it is possible to easily control the work function by using one type of material. Each electrode can be formed.
Further, according to silver nanoparticles, it is possible to form an electrode with one kind of material regardless of whether it is a P-type or N-type organic TFT, and it is possible to improve the performance of each organic TFT. it can.
なお、前記有機電子デバイスにおいて、銀ナノ粒子による電極以外の各層の構成及び材料は、特に限定されるものではなく、従来の有機電子デバイスにおいて公知の態様を適用することができる。 In addition, in the said organic electronic device, the structure and material of each layer other than the electrode by silver nanoparticles are not specifically limited, A well-known aspect is applicable in the conventional organic electronic device.
以下、本発明を実施例に基づいて、さらに具体的に説明する。下記においては、有機電子デバイスのうち、有機ＴＦＴに関して例示するが、本発明は、これに限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples. In the following, an organic TFT among organic electronic devices will be exemplified, but the present invention is not limited to this.
（銀ナノ粒子の製造）
ｎ−ヘキシルアミン５．７８ｇ（５７．１ｍｍｏｌ）とｎ−ドデシルアミン０．８８５ｇ（４．７７ｍｍｏｌ）、Ｎ，Ｎ−ジメチル−１，３−ジアミノプロパン３．８９ｇ（３８．１ｍｍｏｌ）、オレイン酸（＞８５．０％、東京化成工業株式会社）０．２５１ｇ（０．８８９ｍｍｏｌ）を混合し、この混合液にシュウ酸銀７．６０ｇ（２５．０ｍｍｏｌ）を加え、約１時間撹拌し、シュウ酸イオン・アルキルアミン・アルキルジアミン・銀錯化合物の粘性のある固体物を生成させた。これを１００℃で１０分加熱撹拌し、二酸化炭素の発泡を伴う反応を完結させたところ、青色光沢を呈する懸濁液へと変化した。これに、メタノール１０ｍＬを加え、遠心分離により得られた沈殿物を分離し、再度、メタノール１０ｍＬを加え、沈殿物を撹拌し、遠心分離により銀ナノ粒子の沈殿物を得た。
銀ナノ粒子の沈殿物に、ｎ−オクタンとｎ−ブタノールの混合溶媒（体積比１：１ｖ／ｖ）を加えて撹拌し、良好な銀ナノ粒子（粒径５〜２０ｎｍ）の５０重量％分散液を得た。
(Manufacture of silver nanoparticles)
n-hexylamine 5.78 g (57.1 mmol), n-dodecylamine 0.885 g (4.77 mmol), N, N-dimethyl-1,3-diaminopropane 3.89 g (38.1 mmol), oleic acid ( > 85.0%, Tokyo Chemical Industry Co., Ltd.) 0.251 g (0.889 mmol) was mixed, and 7.60 g (25.0 mmol) of silver oxalate was added to this mixture, followed by stirring for about 1 hour, and oxalic acid. A viscous solid of ion, alkylamine, alkyldiamine, and silver complex compound was produced. When this was heated and stirred at 100 ° C. for 10 minutes to complete the reaction accompanied by the foaming of carbon dioxide, the suspension changed to a blue glossy suspension. To this, 10 mL of methanol was added, the precipitate obtained by centrifugation was separated, 10 mL of methanol was added again, the precipitate was stirred, and a precipitate of silver nanoparticles was obtained by centrifugation.
A mixed solvent of n-octane and n-butanol (volume ratio 1: 1 v / v) is added to the silver nanoparticle precipitate and stirred, and 50% by weight of good silver nanoparticles (particle size 5 to 20 nm) is dispersed. A liquid was obtained.
（実施例１）Ｐ型有機ＴＦＴの作製
上記において製造した銀ナノ粒子を用いて、図４に示すような層構造からなるＰ型有機ＴＦＴを作製した。
ガラス基板１上に、銀ナノ粒子の塗布のパターン精度を向上させるため、フッ素系高分子であるテフロン（登録商標）ＡＦ１６００をスピンコート法で、膜厚が５０ｎｍ程度になるように成膜した後、ホットプレート上で１５０℃で１時間焼成した。
その上に、銀ナノ粒子をディスペンサ装置でゲート電極２の形状に塗布しながらパターニングした。そして、１００℃で１時間、基板をホットプレート上で焼成し、塗布された銀ナノ粒子電極を焼結させた。
次に、ゲート絶縁膜３として、フッ素系高分子であるテフロン（登録商標）ＡＦ１６００をスピンコート法で膜厚が２００ｎｍ程度になるように成膜した後、ホットプレート上で１５０℃で１時間焼成した。
その上に、銀ナノ粒子をディスペンサ装置でソース電極４、ドレイン電極５の形状に塗布しながらパターニングした。そして、１００℃で１時間、基板をホットプレート上で焼成し、塗布された銀ナノ粒子電極を焼結させた。ソース電極４、ドレイン電極５は、それぞれ、長さ４５μｍ、幅４７５μｍであった。
この基板を真空蒸着装置にセットし、Ｐ型有機半導体６であるペンタセン（化１）を真空蒸着法で５０ｎｍ成膜し、Ｐ型有機ＴＦＴを作製した。
Example 1 Production of P-type Organic TFT Using the silver nanoparticles produced above, a P-type organic TFT having a layer structure as shown in FIG. 4 was produced.
After the Teflon (registered trademark) AF1600, which is a fluorine-based polymer, is formed on the glass substrate 1 to have a film thickness of about 50 nm by spin coating in order to improve the pattern accuracy of silver nanoparticle application. Baked on a hot plate at 150 ° C. for 1 hour.
On top of this, patterning was performed while applying silver nanoparticles to the shape of the gate electrode 2 with a dispenser device. And the board | substrate was baked on the hotplate at 100 degreeC for 1 hour, and the apply | coated silver nanoparticle electrode was sintered.
Next, after forming Teflon (registered trademark) AF1600, which is a fluorine-based polymer, so as to have a film thickness of about 200 nm as the gate insulating film 3, it is baked on a hot plate at 150 ° C. for 1 hour. did.
On top of this, patterning was performed while applying silver nanoparticles in the shape of the source electrode 4 and the drain electrode 5 with a dispenser device. And the board | substrate was baked on the hotplate at 100 degreeC for 1 hour, and the apply | coated silver nanoparticle electrode was sintered. The source electrode 4 and the drain electrode 5 were 45 μm long and 475 μm wide, respectively.
This substrate was set in a vacuum deposition apparatus, and pentacene (Chemical Formula 1), which is a P-type organic semiconductor 6, was deposited to a thickness of 50 nm by a vacuum deposition method to produce a P-type organic TFT.
作製したＰ型有機ＴＦＴについて、グローブボックス中で特性評価を行った。
その結果、キャリア移動度０．１２ｃｍ2／Ｖｓ、閾値電圧−９Ｖ、オンオフ比６．９×１０4であった。
また、図５に、ゲート−ソース間電圧（ＶＧＳ）が−１０Ｖ、−２０Ｖ、−３０Ｖの場合のドレイン電流とドレイン−ソース間電圧との関係のグラフを示す。
About the produced P-type organic TFT, the characteristic evaluation was performed in the glove box.
As a result, the carrier mobility was 0.12 cm 2 / Vs, the threshold voltage was −9 V, and the on / off ratio was 6.9 × 10 4 .
FIG. 5 is a graph showing the relationship between the drain current and the drain-source voltage when the gate-source voltage (VGS) is −10 V, −20 V, and −30 V.
（実施例２）Ｎ型有機ＴＦＴの作製
上記において製造した銀ナノ粒子を用いて、図４に示すような層構造からなるＮ型有機ＴＦＴを作製した。
ガラス基板１上に、ゲート電極２として、メタルマスクを用いた真空蒸着により、アルミニウムを３０ｎｍ成膜した
次に、ゲート絶縁膜３として、フッ素系高分子であるテフロン（登録商標）ＡＦ１６００をスピンコート法で膜厚が２００ｎｍ程度になるように成膜した後、ホットプレート上で１５０℃で１時間焼成した。
その上に、銀ナノ粒子をディスペンサ装置でソース電極４、ドレイン電極５の形状に塗布しながらパターニングした。そして、１００℃で１時間、基板をホットプレート上で焼成し、塗布された銀ナノ粒子電極を焼結させた。ソース電極４、ドレイン電極５は、それぞれ、長さ１２５μｍ、幅２４０μｍであった。
この基板を真空蒸着装置にセットし、Ｎ型有機半導体６であるＦＰＴＢＢＴ（化２）を真空蒸着法で５０ｎｍ成膜し、Ｎ型有機ＴＦＴを作製した。
(Example 2) Production of N-type organic TFT Using the silver nanoparticles produced above, an N-type organic TFT having a layer structure as shown in FIG. 4 was produced.
On the glass substrate 1, 30 nm of aluminum was deposited as a gate electrode 2 by vacuum deposition using a metal mask. Next, Teflon (registered trademark) AF1600, which is a fluorine-based polymer, was spin-coated as a gate insulating film 3. The film was formed by the method so as to have a film thickness of about 200 nm, and then baked on a hot plate at 150 ° C. for 1 hour.
On top of this, patterning was performed while applying silver nanoparticles in the shape of the source electrode 4 and the drain electrode 5 with a dispenser device. And the board | substrate was baked on the hotplate at 100 degreeC for 1 hour, and the apply | coated silver nanoparticle electrode was sintered. The source electrode 4 and the drain electrode 5 were 125 μm long and 240 μm wide, respectively.
This substrate was set in a vacuum deposition apparatus, and FPTBBT (Chemical Formula 2), which is an N-type organic semiconductor 6, was formed to a thickness of 50 nm by vacuum deposition to produce an N-type organic TFT.
作製したＮ型有機ＴＦＴについて、グローブボックス中で特性評価を行った。
その結果、キャリア移動度０．１ｃｍ2／Ｖｓ、閾値電圧１６Ｖ、オンオフ比４．３×１０3であった。
また、図６に、ゲート−ソース間電圧（ＶＧＳ）が１０Ｖ、２０Ｖ、３０Ｖの場合のドレイン電流とドレイン−ソース間電圧との関係のグラフを示す。
About the produced N type organic TFT, the characteristic evaluation was performed in the glove box.
As a result, the carrier mobility was 0.1 cm 2 / Vs, the threshold voltage was 16 V, and the on / off ratio was 4.3 × 10 3 .
FIG. 6 is a graph showing the relationship between the drain current and the drain-source voltage when the gate-source voltage (VGS) is 10V, 20V, and 30V.
１ 基板
２ ゲート電極
３ ゲート絶縁膜
４ ソース電極
５ ドレイン電極
６ 有機半導体
DESCRIPTION OF SYMBOLS 1 Substrate 2 Gate electrode 3 Gate insulating film 4 Source electrode 5 Drain electrode 6 Organic semiconductor
Claims (6)
当該塗布された銀ナノ粒子の電極を仕事関数に応じた温度で焼成することにより、前記仕事関数を有する銀ナノ粒子の電極を形成する工程と、
を有する有機電子デバイスの製造方法。 Rights Hitoshitsubu diameter of at 30nm or less, the boiling point is covered by a protective molecules near Rua Rukiruamin and boiling in the range of 100 to 250 ° C. is a main component in the near-luer Rukirujiamin range of 100 to 250 ° C. Applying silver nanoparticles as an electrode;
The step of forming the silver nanoparticle electrode having the work function by firing the coated silver nanoparticle electrode at a temperature corresponding to the work function;
The manufacturing method of the organic electronic device which has this .
前記少なくとも１つの電極が、平均粒径が３０ｎｍ以下であり、沸点が１００〜２５０℃の範囲内にあるアルキルアミンと沸点が１００〜２５０℃の範囲内にあるアルキルジアミンを主成分とする保護分子により覆われた銀ナノ粒子を電極として塗布する工程と、
当該塗布された銀ナノ粒子の電極を仕事関数に応じた温度で焼成することにより、前記仕事関数を有する銀ナノ粒子の電極を形成する工程とにより形成されたものである、有機電子デバイス。 An organic electronic device using at least one electrode,
Wherein at least one electrode, the average particle size is at 30nm or less, a boiling point is near Rua Rukiruamin and boiling in the range of 100 to 250 ° C. as a main component in the near-luer Rukirujiamin range of 100 to 250 ° C. Applying silver nanoparticles covered with protective molecules as an electrode;
An organic electronic device formed by firing the coated silver nanoparticle electrode at a temperature corresponding to a work function to form a silver nanoparticle electrode having the work function .
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