DOPING ORGANIC SEMICONDUCTORS
20170279046 · 2017-09-28
Inventors
- Jeremy Burroughes (Cambridge, GB)
- Christopher Newsome (St. Ives, GB)
- Daniel Tobjörk (Hartford, GB)
- Mark Dowling (Elsworth, GB)
Cpc classification
H10K10/46
ELECTRICITY
H10K10/464
ELECTRICITY
International classification
Abstract
We describe a method for reducing a parasitic resistance at an interface between a conducting electrode region and an organic semiconductor in a thin film transistor, the method comprising: providing a solution comprising a dopant for doping said semiconductor, and depositing said solution onto said semiconductor and/or said conducting electrode region to selectively dope said semiconductor adjacent said interface between said conducting electrode region and said semiconductor, wherein depositing said solution comprises inkjet-printing said solution.
Claims
1. A method for reducing a parasitic resistance at an interface between a conducting electrode region and an organic semiconductor in a thin film transistor, the method comprising: providing a solution comprising a dopant for doping said semiconductor, and depositing said solution onto said organic semiconductor and/or said conducting electrode region to selectively dope said organic semiconductor adjacent said interface between said conducting electrode region and said organic semiconductor, wherein depositing said solution comprises inkjet-printing said solution.
2. A method as claimed in claim 1, wherein said conducting electrode region comprises a first conducting electrode region and a second conducting electrode region, and wherein depositing said solution onto said conducting electrode region comprises depositing said solution onto one or both of said first conducting electrode region and said second conducting electrode region.
3. A method as claimed in claim 2, wherein depositing said solution onto both of said first conducting electrode region and said second conducting electrode region comprises depositing a first solution comprising a first dopant onto said first conducting electrode region, and depositing a second solution comprising a second dopant onto said second conducting electrode region.
4. A method as claimed in claim 1, wherein said conducting electrode region comprises a first conducting electrode region and a second conducting electrode region, and wherein depositing said solution onto said organic semiconductor comprises depositing said solution onto a region of said organic semiconductor, wherein said region of said organic semiconductor substantially covers one or both of said first conducting electrode region and said second conducting electrode region.
5. A method as claimed in claim 4, wherein depositing said solution onto said region of said organic semiconductor comprises depositing a first solution comprising a first dopant onto a first region of said organic semiconductor, and depositing a second solution comprising a second dopant onto a second region of said organic semiconductor, wherein said first region of said organic semiconductor substantially covers said first conducting electrode region and said second region of said organic semiconductor substantially covers said second conducting electrode region.
6. A method as claimed in claim 1, wherein said conducting electrode region comprises a first conducting electrode region and a second conducting electrode region, and wherein doping said organic semiconductor comprises doping said semiconductor at a first concentration adjacent an interface between said semiconductor and said first conducting electrode region, and doping said semiconductor at a second concentration adjacent an interface between said semiconductor and said second conducting electrode region.
7. A method as claimed in claim 1, wherein said dopant comprises a solution-processable electron acceptor material.
8. A method as claimed in claim 7, wherein said dopant is any one of Mo(tfd)3, F4-TCNQ or NDP-9.
9. A method for doping an organic semiconductor, the method comprising: providing a substrate, said substrate bearing a conducting source electrode region and a conducting drain electrode region, depositing said organic semiconductor onto said substrate such that said organic semiconductor forms a layer on said substrate which covers said conducting source electrode region and said conducting drain electrode region, printing a solution comprising a dopant onto said organic semiconductor in an area where said organic semiconductor layer substantially covers one or both of said conducting source electrode region and said conducting drain electrode region, to selectively dope said organic semiconductor in said area.
10. A method as claimed in claim 9, the method further comprising: depositing a layer of gate insulator onto said layer of organic semiconductor, and depositing a gate electrode onto said layer of gate insulator.
11. (canceled)
12. A method as claimed in claim 1, wherein said dopant is incorporated into said organic semiconductor with a resolution of higher than 10 μm, preferably higher than 5 μm, more preferably higher than 1 μm.
13. A method of making a sensor or display, said sensor or display comprising a transistor, said transistor comprising a semiconductor, wherein said semiconductor is doped using the method of claim 1.
14. A method as claimed in claim 1, wherein said semiconductor comprises an organic semiconductor.
15. An organic electronic device, wherein a semiconductor layer of said organic electronic device comprises a dopant, and wherein said dopant dopes said semiconductor layer predominantly at an interface between an electrode region of said organic electronic device and said semiconductor layer.
16. An organic electronic device as claimed in claim 15, wherein said organic electronic device is a thin film transistor, and wherein said electrode region is a source and/or drain electrode region.
17. An organic electronic device as claimed in claim 15, wherein said dopant extends through the bulk of said semiconductor layer from said electrode region to an upper surface of said semiconductor layer, and wherein a channel region of said organic electronic device is substantially free of said dopant.
18. An organic electronic device as claimed in claim 15, wherein said electrode region extends beyond said semiconductor layer, wherein said dopant extends from said interface between said electrode region of said organic electronic device and said semiconductor layer to a lateral edge of said semiconductor layer, and wherein a channel region of said organic electronic device is substantially free of said dopant.
19. An organic electronic device as claimed in claim 15, wherein said dopant dopes said semiconductor with a resolution of higher than 10 μm, preferably higher than 5 μm, more preferably higher than 1 μm.
20. An organic electronic device as claimed in claim 15, wherein said semiconductor comprises an organic semiconductor.
21. A sensor or display comprising the organic electronic device as claimed in claim 15.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] These and other aspects of the invention will now be further described by way of example only, with reference to the accompanying figures in which:
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DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0062] In this example, inkjet-printing is used to dope an organic semiconductor in order to reduce a parasitic resistance between an organic semiconductor and conducting source and drain electrode regions, respectively. Here, small molecules and polymers are doped using Mo(tfd)3, F4-TCNQ or NPD-9.
[0063] There is a variety of ways in which to dope the semiconductor using inkjet-printing.
[0064] As illustrated in
[0065] A top-gate, made of a suitable conducting layer, in this example chromium and aluminium, is then deposited on top of the gate insulator. Here, chromium is exploited as an adhesion layer for the insulator.
[0066] It will be understood that the specific materials exploited are merely exemplary, and any other suitable materials may be used when preparing the transistor. Standard fabrication process conditions may be used to prepare the various elements of the transistor.
[0067] In this fabrication route, a standard gate electrode is deposited onto the insulator film, whereby the gate electrode dimension is determined by the size of the aperture in the shadow mask exploited for evaporation. In this example, a common gate for six transistors covers a lateral area of 3 mm×10 mm. Device test cells at 50 mm×50 mm substrate size are used in this example.
[0068] This doping approach reduces the risk of doping the entire channel region or a substantial part thereof. Hence, the parasitic contact resistance is reduced at the interface between the organic semiconductor and the conducting source and drain electrode regions, respectively, without a (substantial) loss in on/off-current ratio.
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[0071] In this fabrication route, additional processing steps are required in order to realise higher resolution gate electrodes. In this example, a positive photoresist (PR), Shipley S1813, is employed to facilitate patterning of the gate by a wet etch process. Standard processes and process conditions may be used to deposit the photoresist onto the gate electrode. As illustrated in
[0072] Alternatively, the photoresist may be removed before the dry etch process is conducted. In this example, the photoresist is removed by a rinsing process in a solvent such as acetone which is a selective solvent for the photoresist and not the insulator.
[0073] It will be understood that the lithography and etching processes may be adapted towards the specific materials used in the thin film transistor.
[0074] A schematic of the resulting patterned transistor structure is illustrated in
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[0076] In order to verify a reduction in parasitic resistance prepared by the methods as outlined above, transport measurements are performed on the transistors.
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[0078] In order to analyse the parasitic resistance, a series of transistors is prepared under identical conditions. The parasitic resistance may then be determined by a transmission line method using a range of channel lengths from, in this example, 5 to 100 μm for the calculation of each of the device sets. An extrapolation of the resistance to zero channel length allows determining the parasitic resistance. The channel width is kept constant for each device at 2 mm.
[0079] The improvement in parasitic resistance when doping the semiconductor as described herein may be analysed by comparing thin film transistors with doped semiconductors to thin film transistors with undoped semiconductors, whereby the devices are prepared under identical conditions.
[0080]
[0081] A third set of devices is prepared in which the host solvent (in this example Dimethyl sulfoxide (DSMO)) for the dopant is deposited at the source and drain electrode regions, whereby no dopant is dissolved in the host solvent. This allows assessing the impact of the printing of the host solvent itself on device performance.
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[0083] In order to obtain the parasitic resistance for the three sets of devices (doped, undoped, and host solvent only printed onto the conducting electrode regions), the transmission line method is used.
[0084] The table in
[0085] It can be seen that in devices with the dopant printed at the conducting source and drain electrode regions, the parasitic resistance is reduced by a factor of approximately 3 compared to undoped reference devices. Furthermore, devices with the dopant printed at the conducting source and drain electrode regions exhibited lower parasitic resistance than those devices with printed host solvent only (i.e. no dopant in the solvent) at the conducting electrode regions.
[0086] The skilled person will appreciate that due to the nature of the process, device data is comparative from sample to sample, because every sample has a different transistor. Hence, fluctuations in performance may reveal differences in output current levels. Nonetheless, a clear trend in improvement of parasitic resistance is observed for devices with dopants incorporated in the semiconductor adjacent the interface between the semiconductor and the respective conducting electrode regions.
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[0088] In order to determine the effect of Mo(tfd)3 doping on the parasitic resistance by applying the transmission line method, thin film transistors with varying channel lengths are prepared.
[0089] The gate-bias dependent parasitic resistance for undoped and Mo(tfd)3-doped transistors is obtained by applying the transmission line method to the data of
[0090] It can be concluded that the improvement in device performance can be attributed to a reduced parasitic resistance between semiconductor and conducting source and drain electrode region, respectively, after doping the semiconductor with Mo(tfd)3.
[0091] Transfer characteristic data corresponding to devices before and after the printing of Mo(tfd)3 dopant at the conducting source and drain electrode regions are shown in
[0092] A further set of reference devices is prepared and tested with the host solvent (in this example DSMO) printed at the conducting electrode regions with device data taken before and after the printing of the solvent. No dopant is dissolved in the solvent. These samples are used to assess if the improved parasitic resistance results obtained may be explained by a solvent annealing effect.
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[0094] The corresponding output characteristics are shown in
[0095] The transmission line method is applied to the data shown in
[0096] The decrease in mobility after deposition of the DSMO solvent only (i.e. without dopant in the solvent) at the conducting electrode regions manifests itself in the device performance as shown in the transfer characteristics of
[0097] The parasitic resistance analysis as well as the output and transfer characteristic data indicate that the improvement in the device performance upon doping the semiconductor is not attributed to a solvent annealing effect.
[0098] Further to the Mo(tfd)3 dopant, devices were prepared using F4-TCNQ as a dopant. In order to compare F4-TCNQ doping to Mo(tfd)3 doping, the same host solvent, DSMO, is used.
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[0100] In order to determine the effect of F4-TCNQ doping on the parasitic resistance by applying the transmission line method, thin film transistors with varying channel lengths are prepared.
[0101] The gate-bias dependent parasitic resistance for undoped and F4-TCNQ-doped transistors is obtained by applying the transmission line method to the data of
[0102] It can be seen that the parasitic resistance decreases by approximately a factor of 1.1 to 1.2 when the semiconductor is doped with F4-TCNQ at the conducting source and drain electrode regions.
[0103] Transfer characteristic data corresponding to devices before and after the printing of F4-TCNQ dopant at the conducting source and drain electrode regions are shown in
[0104] As noted for devices with Mo(tfd)3 dopant solution printed at the conducting electrode regions, devices with F4-TCNQ dopant also exhibit improved output characteristic current levels and reduced parasitic resistance. The improvements in output current levels are similar to those obtained with Mo(tfd)3, i.e. approximately 10 to 15% compared to the same devices prior to the dopant being introduced.
[0105] Inkjet-printing is used in this example as a method for delivering electron acceptor materials for p-type based thin film transistors by using solutions comprising dopants such as Mo(tfd)3 or F4-TCNQ. Inkjet-printing (the one example used here) facilitates the possibility to use the same types of dopants, but may be delivered in a more flexible manner (density of printed features, options for higher resolution deposition, etc.), as outlined above.
[0106] All dopants required may be introduced by a solution method and form bulk films rather than surface treatments of the electrodes for work function shifting. Dopants may be used in an asymmetric fashion as outlined above since the dopant is added after the semiconductor film (or entire device stack) is in place. Asymmetric devices may constitute dopants at only one of the conducting electrode regions and/or different dopant materials for conducting source and drain electrode regions, respectively. Additionally, dopants at different concentrations at different regions of the device are possible with the methods described herein.
Example Fabrication Route A
[0107] Fabrication route A relates to the schematic illustrations of the first example fabrication route for doping a semiconductor as shown in
[0108] The semiconductor used in this example fabrication route is a small molecule/polymer mixture comprising two components. The fraction of each component by mass is: 35% small molecule (see
[0109] The semiconductor mixture is dissolved in a solvent mixture of tetrahydronaphthalene (70% by volume) and ortho-xylene (30% by volume) at a concentration of 10 mg solid to 1 ml solvent.
[0110] The semiconductor mixture is spin coated to a thickness of 49 nm.
[0111] The gate insulator thickness amounts to 287 nm.
[0112] The dopant is NovaLED® NDP-9, which is dissolved in benzonitrile (10 mg solid per 1 ml solvent).
[0113] The printing parameters of the dopant solution in this example are as follows:
[0114] Printing droplets (each droplet has a volume of approximately 8 pl) at a distance of 20 μm over a distance of 2 mm (the entire channel width) at each the source and drain electrodes.
[0115] The gate electrode is a bilayer structure comprising 5 nm chromium and 300 nm aluminium.
Example Fabrication Route B
[0116] Fabrication route B relates to the schematic illustrations of the example fabrication route for doping a semiconductor as shown in
[0117] The semiconductor used in this example fabrication route is a small molecule/polymer mixture comprising two components. The fraction of each component by mass is: 25% small molecule (see
[0118] The semiconductor mixture is dissolved in ortho-xylene at a concentration of 12 mg solid to 1 ml solvent.
[0119] The semiconductor mixture is spin coated to a dried film thickness of 35 nm. The semiconductor film is dried by heating on a hotplate starting from 60 deg C., and ramping the temperature to 80 deg C. over a period of 12 minutes. The temperature is then held at 80 deg C. for a further 5 minutes.
[0120] The gate insulator thickness amounts to 325 nm. The insulator film is dried by heating on a hotplate starting from 60 deg C., and ramping the temperature to 80 deg C. over a period of 12 minutes. The temperature is then held at 80 deg C. for a further 5 minutes.
[0121] The dopants used are Molybdenum tris-[1,2-bis(trifluoromethyl)ethane-1,2-dithiolene (Mo(tfd)3) or 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). Mo(tfd)3 is dissolved in dimethylsulfoxide at a concentration in the range of 2 to 3 mg per 1 ml solvent. F4-TCNQ is dissolved in dimethylsulfoxide at a concentration in the range of 2 to 6 mg per 1 ml solvent.
[0122] The printing parameters of the dopant solution in this example are as follows:
[0123] Printing droplets (each droplet has a volume of approximately 8 pl) at a distance of 100 μm over a distance of 2 mm (the entire channel width) at 200 Hz onto the conducting source electrode region at a substrate temperature of 40 deg C. The substrate is heated, in this example, to enhance the diffusion of the dopant into the semiconductor. The number of repeated interdigitated printing passes at the edge of the gate is 6.
[0124] The gate electrode is a bilayer structure comprising 5 nm germanium and 100-200 nm aluminium.
[0125] The photoresist is a Shipley S1813 resist, which is coated to a thickness of 1500 nm. The photolithography conditions used in this example route are as follows:
[0126] Spin coating of Shipley S1813 photoresist (approximate thickness 1500 nm) and soft-baking at 110 deg C. for 6 minutes in air. The exposure of the photoresist is conducted for 19 seconds at 105 mW/cm.sup.2. The development of the photoresist is conducted by using an aqueous solution of tetramethylammonium hydroxide (2.38%) and subsequent water rinsing at room temperature followed by spin drying to remove excess water from the substrate. The aluminium gate electrode is etched using a sequential process of water rinses and etchant based on an aqueous solution comprising acetic acid (1-10% by volume), nitric acid (1-10% by volume) and phosphoric acid (50-70% by volume). An initial water rinse is followed by etchant and two separate rinse steps at room temperature followed by spin drying to remove excess water from the substrate.
[0127] The dry etching process for the devices is based on an oxygen plasma process (200 W power, 50 seconds) in order to remove the germanium coated insulator and semiconductor films to the source and drain electrode region in the device. After completion of the dry etch process, an acetone spin rinse step is used in order to remove the photoresist layer prior to inkjet-printing. An example image of the gate electrode is shown in
[0128] Overlap distances of the gate electrode to the underlying source and drain electrode regions are typically 40 to 50 μm (to each of the source and drain electrode regions).
[0129] In summary, unlike for electronic doping of inorganic semiconductors by high temperature diffusion and activation, the present process is a low temperature chemical/redox doping process. The dopant is advantageously selectively deposited by inkjet printing after the metal source drain contacts are formed, and the gate electrode is not used as a mask. The dopant is printed on top of metal source and drain electrodes or onto an organic semiconductor (OSC) on top of the metal source and drain electrodes. Thus the dopant stays close to the metal OSC interface after manufacture.
[0130] No doubt many other effective alternatives will occur to the skilled person. It will be understood that the invention is not limited to the described embodiments and encompasses modifications apparent to those skilled in the art and lying within the spirit and scope of the claims appended hereto.