METHOD FOR MANUFACTURING TRANSISTOR ACCORDING TO SELECTIVE PRINTING OF DOPANT
20170200889 ยท 2017-07-13
Assignee
Inventors
Cpc classification
H10D30/6741
ELECTRICITY
H10K10/464
ELECTRICITY
H10D99/00
ELECTRICITY
H10D30/01
ELECTRICITY
H01L21/38
ELECTRICITY
H10K71/30
ELECTRICITY
International classification
H01L21/38
ELECTRICITY
H01L21/04
ELECTRICITY
Abstract
The present invention relates to a method for manufacturing a transistor according selective printing of a dopant. For the manufacture of a transistor, a semiconductor layer is formed on a substrate, and a dopant layer is formed on the semiconductor layer. In the formation of the dopant layer, an inkjet printing is used to selectively print an n type dopant or a p type dopant.
Claims
1. A method for manufacturing a transistor according to selective printing of a dopant, the method comprising: forming a semiconductor layer on a substrate for manufacture of a transistor; and forming a dopant layer on the semiconductor layer, wherein the formation of the dopant layer includes selectively printing an n type dopant or a p type dopant by inkjet printing.
2. The method as claimed in claim 1, wherein the n type dopant comprises at least one selected from the group consisting of cesium fluoride (CsF), bis(ethylenedithio)-tetrathiafulvalence (BEDT-TTF), tetrathianaphthacene (TTN), bis(cyclopentadienyl)-cobalt(II) (CoCp.sub.2), chromium with the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hpp) (Cr.sub.2(hpp).sub.4), tungsten with the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hpp) (W.sub.2(hpp).sub.4), pyronin B chloride, acridine orange base [3,6-bis(dimethylamino)acridine (AOB)], leuco bases like leuco crystal violet (LCV), (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2yl)phenyl)dimethylamine (nDMBI), and 2-(2-methoxyphenyl)-1,3-dimethyl-1H-benzoimidazol-3-ium iodide (o-MeO-DMBI-I), wherein the p type dopant comprises at least one selected from the group consisting of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F.sub.4-TCNQ), 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane (F.sub.2HCNQ), molybdenum trioxide (MoO.sub.3), and tungsten trioxide (WO.sub.3).
3. The method as claimed in claim 1, wherein the n type dopant or the p type dopant is dissolved in a solvent and used in inkjet printing, wherein the solvent comprises any one selected from the group consisting of chlorobenzene, chloroform, trichlorobenzene, tetrahydrofuran, dichlorobenzene, and dichloroethane.
4. The method as claimed in claim 1, wherein the amount of the dopant contained in a portion of the semiconductor layer containing the dopant is 0.5 wt. % to 1.0 wt. %.
5. A method for manufacturing a transistor, comprising: preparing a substrate; forming a source/drain electrode on the substrate; forming a semiconductor layer on the source/drain electrode; forming a dopant layer on the semiconductor layer; forming an insulating layer on the semiconductor layer; and forming a gate electrode on the insulating layer, wherein the formation of the dopant layer is performed by selectively printing a dopant layer on the semiconductor layer by inkjet printing.
6. The method as claimed in claim 5, wherein the n type dopant comprises at least one selected from the group consisting of cesium fluoride (CsF), bis(ethylenedithio)-tetrathiafulvalence (BEDT-TTF), tetrathianaphthacene (TTN), bis(cyclopentadienyl)-cobalt(II) (CoCp.sub.2), chromium with the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hpp) (Cr.sub.2(hpp).sub.4), tungsten with the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hpp) (W.sub.2(hpp).sub.4), pyronin B chloride, acridine orange base [3,6-bis(dimethylamino)acridine (AOB)], leuco bases like leuco crystal violet (LCV), (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2yl)phenyl)dimethylamine (nDMBI), and 2-(2-methoxyphenyl)-1,3-dimethyl-1H-benzoimidazol-3-ium iodide (o-MeO-DMBI-I), wherein the p type dopant comprises at least one selected from the group consisting of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F.sub.4-TCNQ), 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane (F.sub.2HCNQ), molybdenum trioxide (MoO.sub.3), and tungsten trioxide (WO.sub.3).
7. The method as claimed in claim 5, wherein the n type dopant or the p type dopant is dissolved in a solvent and used in inkjet printing, wherein the solvent comprises any one selected from the group consisting of chlorobenzene, chloroform, trichlorobenzene, tetrahydrofuran, dichlorobenzene, and dichloroethane.
8. The method as claimed in claim 5, wherein the amount of the dopant contained in a portion of the semiconductor layer containing the dopant is 0.5 wt. % to 1.0 wt. %.
9. The method as claimed in claim 5, wherein the semiconductor layer comprises any one selected from the group consisting of an organic semiconductor, a metal oxide semiconductor and a carbon compound semiconductor.
10. The method as claimed in claim 9, wherein the organic semiconductor comprises any one selected from the group consisting of an amphiphilic organic semiconductor, an n type organic semiconductor and a p type organic semiconductor, wherein the amphiphilic organic semiconductor is any one selected from the group consisting of [6,6-phenyl-C.sub.61-butyric acid methyl ester (PCBM), naphthalene-bis(dicarboximide)bithiophene (P(NDI.sub.2OD-T.sub.2)), poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F.sub.8BT), poly(9,9-dioctylfluorene) (PFO), diketopyrrolo-pyrrole-bithiophene (DPPT-TT), and poly(thienylenevinylene-cophthalimide) (PTVPhI-Eh) functionalized with dodecyl at the imide nitrogen, wherein the n type organic semiconductor is any one selected from a substance based on acene, fully fluorinated acene, partially fluorinated acene, partially fluorinated oligothiophene, fullerene, fullerene with a substituent, fully fluorinated phthalocyanine, partially fluorinated phthalocyanine, perylene tetracarboxylic diimide, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic diimide, or naphthalene tetracarboxylic dianhydride, or a derivative thereof, wherein the P type organic semiconductor is any one selected from a substance including acene, poly-thienylene vinylene, poly-3-hexylthiophene, alpha-hexathienylene, naphthalene, alpha-6-thiophene, alpha-4-thiophene, rubrene, polythiophene, polyparaphenylene vinylene, polyparaphenylene, polyfluorene, polythiophene vinylene, polythiophene-heterocyclic aromatic copolymer, or triaryl amine, or a derivative thereof.
11. The method as claimed in claim 9, wherein the metal oxide semiconductor is any one selected from the group consisting of zinc oxide (ZnO.sub.x), indium oxide (InO.sub.x), indium gallium zinc oxide (IGZO), and indium tin oxide (ITO).
12. The method as claimed in claim 9, wherein the carbon compound semiconductor is selected from carbon nanotube (CNT) or graphene nano-ribbon.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0025]
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
BEST MODES FOR CARRYING OUT THE PRESENT INVENTION
[0032] Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Reference should be made to the drawings, in which the same reference numerals are used throughout the different drawings to designate the same or similar components as possible. Further, in the following description of the present invention, a detailed description of known configurations and functions incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
[0033] The term about or approximately or substantially used in this specification are intended to have meanings close to numerical values or ranges specified with an allowable error and to prevent accurate or absolute numerical values disclosed for understanding of the present invention from being illegally or unfairly used by any unconscionable third party.
[0034] The transistor of the present invention is described in association with the top gate bottom contact (TGBC) structure, but it can be applied to the bottom gate top contact (BGTC) structure as well.
[0035]
[0036] A top gate type transistor is manufactured in the steps of preparing a substrate; forming source/drain electrodes to be disposed apart from each other on the substrate; forming a semiconductor layer to cover the source/drain electrodes; forming a dopant layer on the semiconductor layer; forming an insulating layer on the dopant layer; and forming a gate electrode in a partial region on the insulating layer.
[0037] The transistor of the present invention may be used for the CMOS inverter device comprising both n type and p type semiconductors.
[0038] Referring to
[0039] The substrate may include a transparent substrate like glass, or a flexible substrate, such as a silicone substrate, a plastic substrate or a metal foil substrate. Examples of the plastic substrate as used herein may include polyether sulphone, polyacrylate, polyether imide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide, polyallylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, etc.
[0040] The source/drain electrodes may be formed as a single layer selected from Au, Al, Ag, Mg, Ca, Yb, Cs-ITO, or alloy thereof; or as a multi-layer that further includes an adhesive metal layer like Ti, Cr or Ni in order to enhance the adhesion to the substrate. Moreover, graphene, carbon nanotube (CNT), PEDOT:PSS conductive polymer, silver nanowire, etc. can be used to manufacture a device having much higher elasticity than the existing metals. These substances can also be used as an ink for the printing process like ink-jet printing or spraying to make source/drain electrodes. Using the printing process to form source/drain electrodes enables it to exclude the vacuuming process, ending up reducing the production cost.
[0041] On the source/drain electrodes may be formed a semiconductor layer. The semiconductor layer may comprise any one selected from an organic semiconductor, a metal oxide semiconductor, and a carbon compound semiconductor.
[0042] The organic semiconductor as used herein may be an amphiphilic organic semiconductor, an n type organic semiconductor, or a p type organic semiconductor.
[0043] The amphiphilic organic semiconductor as used herein may be any one selected from the group consisting of [6,6-phenyl-C.sub.61-butyric acid methyl ester (PCBM), naphthalene-bis(dicarboximide)bithiophene (P(NDI.sub.2OD-T.sub.2)), poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F.sub.8BT), poly(9,9-dioctylfluorene) (PFO), diketopyrrolo-pyrrole-bithiophene (DPPT-TT), and poly(thienylenevinylene-cophthalimide) (PTVPhI-Eh) functionalized with dodecyl at the imide nitrogen.
[0044] The n type organic semiconductor as used herein may be any one selected from the substances based on acene, fully fluorinated acene, partially fluorinated acene, partially fluorinated oligothiophene, fullerene, fullerene with a substituent, fully fluorinated phthalocyanine, partially fluorinated phthalocyanine, perylene tetracarboxylic diimide, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic diimide, or naphthalene tetracarboxylic dianhydride. In this regard, the acene-based substance may be selected from anthracene, tetracene, pentacene, perylene, or coronene.
[0045] Further, the p type organic semiconductor as used herein may be selected from a substance including acene, poly-thienylene vinylene, poly-3-hexylthiophene, alpha-hexathienylene, naphthalene, alpha-6-thiophene, alpha-4-thiophene, rubrene, polythiophene, polyparaphenylene vinylene, polyparaphenylene, polyfluorene, polythiophene vinylene, polythiophene-heterocyclic aromatic copolymer, or triaryl amine, or a derivative thereof. In this regard, the acene-based substance is any one of pentacene, perylene, tetracene, or anthracene.
[0046] Further, the metal oxide semiconductor as used herein may be any one selected from the group consisting of zinc oxide (ZnO.sub.x), indium oxide (InO.sub.x), indium gallium zinc oxide (IGZO), and indium tin oxide (ITO).
[0047] Further, the carbon compound semiconductor as used herein may be selected from carbon nanotube (CNT) or graphene nano-ribbon.
[0048] The semiconductor layer is formed on the source/drain electrodes by spin coating, spraying, inkjet printing, flexography, screening, dip coating, gravure printing, etc. This method enables it to form patterns on the electrodes or in a local region of the substrate and to perform a thermal treatment or exposure after formation of the organic semiconductor layer in order to enhance the performance of the device, including semiconductor crystallinity, stability, etc.
[0049] Subsequently, the present invention may form a dopant layer selectively in a part of the region where the organic semiconductor layer is disposed, in the step of forming a dopant layer.
[0050] Forming a dopant layer means that the solvent containing a dopant dissolves the semiconductor layer to turn the region making up a part of the semiconductor layer into a dopant layer.
[0051] At this point, the inkjet printing method is used to form a dopant layer on a part of the semiconductor layer.
[0052] It is a conventional technique to form a device, such as an electrode, a semiconductor layer, etc., by inkjet printing. Yet, the present invention employs an inkjet printing method using a solvent as ink to form a dopant layer in the dopant formation process that is removing an unnecessary portion.
[0053] The present invention uses the inkjet printing method to form a dopant layer in a local region. That is, the formation of a dopant layer can be performed locally in the region as possible as the current inkjet printing technique allows. Hence, the dopant layer can be formed in a region that is from about 1 m up to a desired size, preferably 1 m to 10 mm in diameter. It is technically difficult to use other printing methods than the inkjet printing technique in order to selectively form a dopant layer on the semiconductor layer.
[0054] In the present invention, the substance available as a dopant may be an n type dopant or a p type dopant.
[0055] Examples of the n type dopant as used herein may include cesium fluoride (CsF), bis(ethylenedithio)-tetrathiafulvalence (BEDT-TTF), tetrathianaphthacene (TTN), bis(cyclopentadienyl)-cobalt(II) (CoCp.sub.2), chromium with the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hpp) (Cr.sub.2(hpp).sub.4), tungsten with the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hpp) (W.sub.2(hpp).sub.4), pyronin B chloride, acridine orange base [3,6-bis(dimethylamino)acridine (AOB)], leuco bases like leuco crystal violet (LCV), (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2yl)phenyl)dimethylamine (nDMBI), 2-(2-methoxyphenyl)-1,3-dimethyl-1H-benzoimidazol-3-ium iodide (o-MeO-DMBI-I), etc.
[0056] Examples of the p type dopant as used herein may include 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F.sub.4-TCNQ), 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane (F.sub.2HCNQ), molybdenum trioxide (MoO.sub.3), tungsten trioxide (WO.sub.3), etc.
[0057] On the other hand, it is necessary to use a solvent that dissolves a dopant in order to print the dopant by the inkjet printing technique. The preferred solvent is the one that dissolves all of the dopant and part of the semiconductor layer.
[0058] Examples of the solvent as used herein may include chlorobenzene, chloroform, trichlorobenzene, tetrahydrofuran, dichlorobenzene, and dichloroethane.
[0059] Preferably, the mixing ratio of the dopant to the solvent in the inkjet printing method ranges from 0.5 mg/ml to 1.5 mg/ml.
[0060] When the mixing ratio of the dopant to the solvent with respect to the semiconductor is less than 0.5 mg/ml, an effective doping is impossible to achieve, resulting in insignificant or little change in the performance of the device. When the mixing ratio of the dopant to the solvent is greater than 1.5 mg/ml, it makes an adverse effect on the crystallinity of the semiconductor film to deteriorate the performance of the device or excessively raise the conductivity, causing a malfunction of the transistor.
[0061] Referring to
[0062] In the part of the semiconductor layer containing the dopant, the amount of the dopant is preferably in the range of 0.5 wt. % to 1.0 wt. %.
[0063] In the part of the semiconductor layer containing the dopant, the quantity of the dopant is preferably in the range of 0.5 wt. % to 1.0 wt. %.
[0064] The quantity of the dopant ranging from 0.5 wt. % to 1.0 wt. % secures high performance of the device, that is, high conductivity without adversely affecting the crystallinity of the semiconductor film.
[0065]
[0066] In
[0067] As can be seen from the graph (a) of
[0068] As can be seen from the graph (b) of
[0069] An insulating layer may be formed on the whole surface of the organic semiconductor layer on which the dopant layer is printed, in the step of forming an insulating layer.
[0070] The insulating layer may comprise a single layer or a multi-layer of an organic or inorganic insulating layer; or an organic-inorganic hybrid layer. The organic insulating layer may use at least one selected from the group consisting of polymethylmethacrylate (PMMA), polystyrene (PS), phenol-based polymer, acryl-based polymer, imide-based polymer like polyimide, arylether-based polymer, amide-based polymer, fluorine-based polymer, p-xylene-based polymer, vinylalcohol-based polymer, and perylene. The inorganic insulating layer may use at least one selected from the group consisting of silicon oxide, silicon nitride, Al.sub.2O.sub.3, Ta.sub.2O.sub.5, BST, and PZT.
[0071] On a part of the region of the insulating layer may be formed a gate electrode, in the step of forming a gate electrode.
[0072] The gate electrode may comprise any one selected from the group consisting of aluminum (Al), Al-alloy, molybdenium (Mo), Mo-alloy, silver nanowire, gallium indium eutectic, and PEDOT:PSS. The gate electrode may be prepared through the printing process, such as ink-jet printing or spraying, using the above-mentioned substances as ink. Using the printing process to form the gate electrode can exclude the vacuuming process and thus reduce the production cost.
[0073] In this manner, the transistor according to one embodiment of the present invention is completed.
[0074]
[0075]
[0076] On the contrary, the graph in blue is for the device of the present invention doped by inkjet printing. Unlike the graph of the undoped inverter, the graph shows the voltage loss almost as low as zero when Vin=60 V or 0 V, that is, good inverter characteristics without hysteresis. Besides, the doped inverter exhibits a higher voltage gain characteristic of about 14 than the undoped inverter.
MODES FOR CARRYING OUT THE INVENTION
[0077] Hereinafter, a detailed description will be given as to specific embodiments of the present invention.
Example 1
[0078] Preparation of Substrate and Formation of Electrodes
[0079] In the manufacture of a transistor, a substrate is prepared and source/drain electrodes are formed on the substrate.
[0080] Formation of Semiconductor Layer
[0081] An organic semiconductor, PCBM, is used to form an organic semiconductor layer. In the formation of the organic semiconductor layer, the semiconductor layer is formed to cover both the source and drain electrodes.
[0082] Formation of Dopant Layer
[0083] In order to form a dopant layer, an n type dopant is mixed with chlorobenzene prepared as a solvent to prepare an n type dopant solution. The n type dopant is cesium fluoride (CsF), and the concentration of the dopant is 1 mg/ml in the solution.
[0084] The dopant solution is printed on the semiconductor layer by inkjet printing so that a dopant layer is formed using an n type dopant, CsF, on the semiconductor layer in the region between the source and drain electrodes. The inkjet printing is performed to print a dopant layer as large as about 50 m in diameter.
[0085] The dopant layer is formed so that the quantity of the dopant injected into the semiconductor layer amounts to 1.0 wt. %. The quantity of the dopant can be controlled by adjusting the amount of the solution injected by the inkjet printing method.
[0086] Formation of Insulating Layer
[0087] Spin coating is performed using polystyrene (PS) to form an insulating layer on the substrate including the organic semiconductor layer.
[0088] Formation of Gate Electrode
[0089] A gate electrode is formed on a part region of the insulating layer. This process can be performed by deposition of aluminum Al.
[0090] In this manner, a transistor is fabricated.
Examples 2 and 3
[0091] The procedures are performed in the same manner as described in Example 1, excepting that the quantity of the n type dopant, CsF, of the semiconductor layer as used in the step of forming a dopant layer is 0.5 wt. % (Example 2) or 0.1 wt. % (Example 3).
Example 4
[0092] The procedures are performed to manufacture a transistor in the same manner as described in Example 1, excepting that a p type dopant, F.sub.4-TCNQ, is used to form a dopant layer on the semiconductor layer in a region between the source and drain electrodes, where the quantity of the dopant injected into the semiconductor layer is 1.0 wt. %.
Examples 5 and 6
[0093] The procedures are performed in the same manner as described in Example 4, excepting that the quantity of the p type dopant, F.sub.4-TCNQ, of the semiconductor layer as used in the step of forming a dopant layer is 0.5 wt. % (Example 5) or 0.1 wt. % (Example 6).
Comparative Example 1
[0094] The procedures are performed in the same manner as described in Example 1, excepting that a thin film transistor is manufactured without forming a dopant layer using the inkjet printing method.
[0095]
[0096] In
[0097]
[0098] The graphs of
[0099] As can be seen from the graphs (a) and (b) of
Example 7
[0100] 13 nm/2 nm-thick Au/Ni source and drain electrodes are patterned on a Corning Eagle 2000 glass substrate by a general photolithography process. Prior to the fabrication of an OTFT, the substrate is immersed in the solvents of distilled water, acetone and isopropyl alcohol in sequential order and then washed in an ultra-sonification bath for 10 minutes. The substrate is sufficiently dried out through nitrogen gas to completely eliminate the remaining solvent and then surface-washed again with UV/O.sub.3 equipment.
[0101] A semiconductor ink that is prepared by dissolving 10 mg/mL of P(NDI.sub.2OD-T.sub.2) (Polyera Inc.) (Chemical Formula 1) in a solvent of chlorobenzene is applied by spin coating to form a film on the substrate on which the source and drain electrodes are formed. For the preparation of the dopant ink, an organic compound of bis(cyclopentadienyl)-cobalt(II) (cobaltocene, CoCp.sub.2) (Sigma-Aldrich Inc.) (Chemical Formula 2) as a dopant is dissolved in a 1:1 mixed solvent of 2-ethoxyethanol and chlorobenzene.
##STR00001##
[0102] For the sake of inkjet doping, the dopant ink thus prepared is applied selectively to a channel region of the substrate including the semiconductor film with an inkjet printer. The selectively doped semiconductor film is subjected to a thermal treatment at 150 C. for 20 minutes. Finally, a PMMA (Sigma-Aldrich Inc.) insulator is applied to a thickness of 500 nm by spin coating, and an Al electrode is formed as thick as 50 nm using thermal deposition equipment to complete a top gate type OTFT.
Comparative Example 2
[0103] The procedures are performed in the same manner as described in Example 7, excepting that an OTFT having the same structure of Example 7 is manufactured without inkjet doping.
[0104]
[0105]
[0106] In
[0107] The undoped device of Comparative Example 2 is under stress from the continuous operations, which changes the transition curve towards the lower level of the threshold voltage. Yet, the doped device of Example 7 forms a constant transition curve without a change against long-term operations. This shows that the present invention is under nearly no stress from the long-term continuous operations.
[0108] The foregoing description of the invention has been presented for purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching.