The present invention is related to thin film transistors and approaches for fabricating thin film transistors.
Thin film transistors (TFTs), particularly those made of organic semiconductor materials, are of interest for use in flat panel displays and in many other applications. For example, flat panel displays based on organic TFTs can have lower fabrication costs when compared to TFTs fabricated using inorganic materials. Organic-based transistors have the potential to allow fabrication of large area displays and other devices that provide both high performance and low cost. However, at the present time, devices made with inorganic components significantly outperform their organic-based counterparts.
Among currently used materials for fabrication of TFTs, small molecule and solution-based polymeric organic materials are of particular interest. Typically, small molecule organic materials have low solubility in organic solvents and thus fabrication of useful TFTs requires relatively expensive manufacturing processes, such as vacuum deposition and/or photolithography. Solution-based organic transistors cost less to fabricate because they are amenable to processing using inexpensive coating and patterning techniques. Thus, solution-based organic TFTs provide an attractive option for use in large area or disposable devices.
Improved performance and fabrication processes for organic or inorganic thin film transistors are desirable. The present invention fulfils these and other needs, and offers other advantages over the prior art.
Embodiments of the invention are directed to thin film transistors and approaches for fabricating thin film transistors. One embodiment is directed to a thin film field effect transistor. The transistor includes an active layer comprising a semiconductor. Gate, source, and drain contacts are electrically coupled to the active layer. A gate dielectric is arranged in relation to the gate contact. A layer of discontinuous conductive clusters is arranged between the gate dielectric and the active layer.
Another embodiment of the invention is directed to a thin film field effect transistor having an active layer comprising a semiconductor material and carbon nanotubes. Gate, source, and drain contacts are electrically coupled to the active layer. A dielectric material is arranged relative to the gate contact. A layer of discontinuous conductive material is arranged between the dielectric material and the active layer.
A further embodiment of the invention involves a method for fabricating thin film transistors having gate, source and drain contacts. An active layer comprising a semiconductor is formed. A dielectric layer is formed between the active layer and the gate contact of the transistor. A layer of discontinuous conductive clusters is formed between the dielectric and the active layer.
The above summary of the present invention is not intended to describe each embodiment or every implementation of the present invention. Advantages and attainments, together with a more complete understanding of the invention, will become apparent and appreciated by referring to the following detailed description and claims taken in conjunction with the accompanying drawings.
While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It is to be understood, however, that the intention is not to limit the invention to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the scope of the invention as defined by the appended claims.
In the following description of the illustrated embodiments, reference is made to the accompanying drawings that form a part hereof, and in which are shown by way of illustration, various embodiments in which the invention may be practiced. It is to be understood that the embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
Organic-based thin film transistors provide a relatively low-cost option for fabrication of disposable and/or large area electronic devices. Several types of semiconductors are presently used for making electronic devices. Small molecule organic semiconductors and solution-based polymeric organic semiconductors are two examples. Typically, small molecule organics have low solubility in organic solvents and thus require vacuum deposition or other relatively expensive techniques to form films. Shadow mask or photolithographic methods are used to pattern multiple layers to make useful devices. Vacuum deposition, shadow mask, and photolithography are relatively more expensive fabrication processes when compared to processes available for the solution-based polymeric semiconductors.
Solution-based organic TFTs have the potential to allow the lowest fabrication cost among organic semiconductor types because devices can be formed using less expensive coating and patterning processes. For example, deposition of the films may be accomplished by spin coating, knife-coating, roll-to-roll web-coating, dip coating, and other techniques. The solution-based organic devices can be patterned by ink-jet printing, gravure printing, or screen printing, for example.
The performance of solution-based organic transistors is usually lower than vacuum deposited small-molecule-based transistors. It is desirable to improve the performance of TFTs of all types, particularly organic TFTs having the potential to provide low cost electronic devices.
The effect of lower carrier mobility exhibited by organic semiconductor materials, in particular solution-based organics, is exacerbated when coupled with inexpensive TFT fabrication methods, such as printing processes. The limited feature size resolution of some inexpensive patterning processes can preclude fabrication of electronic devices with a sufficiently short channel to provide a useful device. For example, the feature size resolution of some processes may be greater than 20 microns. Thus, it is desirable to develop structures that compensate for the relatively longer channel produced by inexpensive fabrication processes.
Embodiments of the invention are directed to approaches that enhance organic or inorganic TFT performance, particularly the performance of organic TFTs, including solution-based organic TFTs. The techniques described herein produce solution-based organic TFTs that have comparable performance to organic TFTs formed using vacuum-deposited small-molecule materials.
Embodiments of the invention are directed to TFT devices that include a layer of 2-D discontinuous electrically conductive clusters or islands at the interface between the gate dielectric and the active layer. The 2-D discontinuous conductive clusters can also be present in the active layer or on top of the active layer or in the gate dielectric. The transistor structure 100 of
While not bound by any particular theory, one explanation for the performance of TFTs constructed with interfacial conductive clusters is that the layer of conductive clusters 110 modifies the transport mechanism of the carriers in the channel region of the TFT. The thin layer of conductive clusters 110 allows some of the carriers in the TFT channel region near the dielectric-semiconductor interface to flow ballistically for a portion of their path across the channel. Arrows 160, indicate the path of carriers that flow ballistically within the conductive clusters 110. Carriers that flow ballistically in this manner avoid the relatively slower transport processes through the semiconductor active layer that involve hopping and scattering in molecules. The presence of conductive clusters 110 in the channel region between the dielectric 140 and the semiconductor layer effectively reduces the channel length, increases carrier mobility, and increases transconductance of the TFT. The conductive clusters 110 may also serve to reduce the charge trapping process in the semiconductor material of the active layer.
The configuration illustrated in
The addition of a layer of conductive clusters at the dielectric/semiconductor interface to enhance device properties is counterintuitive because the presence of impurities at the semiconductor junction is known to degrade junction characteristics in other transistor technologies. For example, impurities at the gate-semiconductor junction are known to increase leakage current and degrade the ON/OFF current ratio. However, without being bound to theory, particularly in the case of solution-based organic TFTs, the thin interfacial layer of conductive clusters appears to make the overall carrier transport process more efficient, thus improving transistor characteristics. The improvement in carrier mobility is most pronounced in solution-based polymeric semiconductors, presumably because these semiconductor materials have a relatively low carrier mobility which can be improved significantly by the addition of the conductive clusters.
Furthermore, conductive clusters at the gate dielectric-active layer interface unexpectedly alter the wetting properties of the semiconductor on the dielectric film. The presence of the thin layer of conductive clusters significantly improves contact between the dielectric film and the semiconductor material during fabrication of the TFTs. In addition, TFTs having the conductive cluster interface layer showed enhanced repeatability when sequential scans of drain current (Id) vs. gate voltage (Vg) were conducted. The threshold voltage was more repeatable in TFTs having a layer of conductive clusters when compared with TFTs without the conductive cluster layer.
One example of TFT formation involves the formation of the gate metallization electrode, followed by formation of the gate dielectric film on the gate metallization electrode. An ultra-thin layer of predominantly non-carbon metallic clusters is formed on a gate dielectric film. An active layer comprising an organic semiconductor is coated or printed on the metallic cluster surface, followed by the formation of source and drain electrodes to form top-contact TFTs.
Processes and structures that use a thin layer of discontinuous conductive clusters at the dielectric-semiconductor interface are especially compatible with low cost patterning methods, such as printing processes, that have limited resolution. The layer of conductive clusters can effectively shorten the channel length from the physically long channel length produced by printing. Therefore, the use of a thin layer of conductive clusters at the dielectric-semiconductor interface at least partially compensates for the lower resolution of inexpensive patterning methods.
The active layer, which may include one or more material layers, comprises an organic semiconductor, such as a small molecule organic semiconductor or solution-based organic semiconductor or a blend of organic semiconductor and a polymer or inorganic semiconductors. In one embodiment, the active layer may comprise a low molecular weight organic semiconductor. In another embodiment, the active layer may comprise a polymeric organic semiconductor. In another embodiment, the active layer may include a blend of an organic semiconductor and a polymer.
In some embodiments, carbon nanotubes are dispersed in the semiconductor material or semiconductor and polymer blended material to form non-continuous, 3-D conducting paths in the active layer. Several examples of suitable materials for the active layer are provided in more detail below.
There are many options for selecting materials for the conductive clusters, which may comprise predominantly non-carbon metallic materials, metals or metal oxides, for example. The selection of the cluster material preferably takes into account the type of semiconductor used to form the active layer. It is desirable to form an ohmic contact between the conductive cluster and the organic semiconductor. For example, for p-type semiconductors, selection of the cluster material can be made from high work function materials, such as gold, palladium, platinum, etc. For n-type semiconductors, selection may be made from low work function materials, such as aluminum, silver, calcium, etc. The cluster material may comprise carbon nanotubes (CNTs). A very dilute CNT dispersion with or without the electrically conductive clusters can be coated on a surface to form discontinuous conducting paths. The work function of CNTs allows formation of an ohmic contact with most of the p-type organic semiconductors.
In some embodiments the interfacial layer of conductive clusters may include multiple sub-layers. For example, an interfacial layer may include a first sub-layer of a first material and a second sub-layer of a second material. The material, characteristics and/or physical dimensions of the clusters of the sub-layers may be the same, or the clusters of one sub-layer may have materials, characteristics and/or dimensions that differ from the materials, characteristics and/or dimensions of the clusters of another sub-layer.
As previously discussed, TFTs having interfacial conductive clusters exhibit better repeatability when sequential scans of Id vs. Vg are conducted. The threshold voltage varies less for TFTs containing conductive clusters than for TFTs without the conductive clusters. In addition, higher carrier mobility and ON/OFF current ratio can be obtained for TFTs containing conductive clusters when compared with their counterparts without conductive clusters.
Some embodiments of the invention employ an interfacial layer of conductive clusters along with carbon nanotubes dispersed in the semiconductor material. The TFT configuration illustrated in
Without being bound by any particular theory, a partial conducting network via the metallic portion of SWCNTs in a semiconductor matrix effectively reduces the channel length between source and drain because carriers are able to flow ballistically through SWCNTs, without going through the typical hopping/scattering transport processes as in an organic semiconductor without the SWCNTs. Therefore, the inclusion of SWCNTs in the active layer effectively increases carrier mobility and transconductance of the TFT.
The operating parameters of TFTs that incorporate dispersed SWCNTs may be enhanced through control of the material composition of the active layer. The distribution of the SWCNT lengths in SWCNTs purchased from commercial suppliers is very broad. The loading percentage of SWCNTs incorporated into the matrix may vary based on the characteristics of the SWCNTs obtained. The SWCNTs should be well-dispersed in the organic semiconductor matrix. Bundles of SWCNTs in the matrix can deteriorate TFT performance.
Dispersion of even a minimal percentage of SWCNTs into an organic semiconductor active layer matrix, often produces a blended solution that cannot wet the dielectric substrate. Wetting the dielectric substrate is necessary for deposition of the active layer to form a transistor. The inclusion of a thin layer of conductive clusters, e.g., a layer having a thickness of about 10 Å or about 5 Å, at the dielectric-active layer interface can dramatically improve the wetting of the blended SWCNT/organic semiconductor solution and result in a high yield of TFTs. The combination of an interfacial layer of conductive clusters and a blended active layer material including SWCNTs in the organic semiconductor solution produces a high yield of robust organic TFTs. Solution-based top contact TFTs have shown carrier mobility greater than 1.3 cm2/V·s, ON/OFF current ratio of greater than 7×103 and drain current greater than 10−4 amps.
As previously discussed, the incorporation of an interfacial layer of dispersed conductive clusters improves the carrier mobility and transconductance of organic-based TFTs with or without SWCNTs. In addition, higher ON/OFF current ratio and better stability of threshold voltage at repeatable scanning of source drain current vs. gate voltage have been observed. A beneficial by-product of inserting the metallic clusters on the dielectric layer is an improvement in wetting characteristics for the subsequent coating of the semiconductor solution. Because of the cluster nature of the interfacial layer, no continuous conducting paths are formed by the clusters in a two-dimensional space. By controlling the thickness of the metallic layer, and thus the size and density of the clusters, the leakage current can be reduced.
Fabrication of TFTs using an interfacial layer of conductive clusters and an active layer that does not include carbon nanotubes has certain advantages. For example, SWCNTs are expensive and their dimensions can vary from supplier to supplier, making control over the device characteristics more complex. However, the incorporation of SWCNTs in the semiconductor matrix in addition to an interfacial layer of conductive clusters at the dielectric-semiconductor interface further improves device performance. For example, solution-based top contact TFTs using both the interfacial layer along with SWCNT dispersed in the semiconductor layer have shown enhanced mobility ON/OFF current ratio and drain current.
For TFTs without SWCNTs, three kinds of p-type organic semiconductors, designated herein as Å, B, and C, were tested on substrates having 5 Å or 10 Å gold clusters that were vacuum deposited on hexamethyldisilazane (HMDS) treated SiO2/p-Si/Al or SiO2/n+-Si/Al surface and on the same substrates with only HMDS treated SiO2/p-Si/Al surface or bare SiO2/n+-Si/Al. HMDS assists in molecular ordering so that organic semiconductors may be more conductive when biased with voltage.
Each of the three types of organic semiconductor materials, A, B, and C were dissolved in dichlorobenzene (DCB). The chemical structure of the three materials is shown in the boxes below.
A. Poly(3,4-dihexylthiophene-alt-2,6-anthracene)—1.2 wt % of A dissolved in DCB
B. Poly(3,4-ethylenedioxy-2,5-thiophene-alt-9,10-bis[(triisopropylsilyl)ethynyl]-2,6-anthracene)-2 wt % of B dissolved in DCB.
C. TIPS-pentacene—1 wt % of C and 2.5 wt % of polystyrene dissolved in DCB.
The gold clusters deposited on HMDS treated SiO2 enhanced wet out of all three solution-based organic semiconductors. In the areas without gold clusters, wetting of the three organic solutions was either poor or would not wet the surface at all. The same effect was observed for spin coated organic semiconductors on substrates that have both gold clusters on HMDS treated SiO2 and HMDS treated SiO2 only.
Example 1 illustrates the discontinuous configuration of the conductive clusters forming the interfacial layer. A layer of gold clusters about 10 Å thick was vacuum deposited on HMDS treated SiO2 surface. Tapping mode was used for taking the atomic force microscope (AFM) image of this surface as shown in
Example 2 illustrates the higher mobility of TFTs having an interfacial layer of conductive clusters when compared to similar TFTs without the interfacial layer. TFTs with the same channel width and length (W/L) made from organic semiconductor solution B with and without 10 Å of gold clusters were fabricated.
An improvement for these two parameters has also been observed for TFTs using organic semiconductor solution C as the active layer.
Hole transport in the channel is via ballistic movement when the carriers enter the gold cluster regions that form an ohmic contact with the organic semiconductor. Hopping by holes among different organic molecules and scattering in the amorphous structure does not occur during the time that the carriers are in gold clusters. Thus, the size and density of the gold clusters contribute to the percentage that the travel time of the conductors can be shortened. The decrease in the travel time of the conductors can also be expressed as an effective reduction in channel length.
Example 3 illustrates the superior repeatability of TFTs having an interfacial layer of conductive clusters when compared to similar TFTs without the interfacial layer. A TFT was fabricated having top source and drain contacts (W/L=1120 μm/110 μm) patterned by depositing ˜800 Å of gold through a Kapton shadow mask on organic semiconductor Å which was spun on 10 Å of gold clusters deposited on HMDS treated SiO2 surface.
In contrast, the same organic semiconductor solution A was spun on only HMDS treated SiO2 surface for forming a TFT having the same W/L ratio as previously constructed but without the interfacial gold clusters.
Example 4 illustrates the effect of an interfacial layer of conductive clusters on channel length.
For a given thickness of the vacuum deposited ultra-thin gold on a given surface, the statistical distribution of cluster size and density is largely predetermined. There is an optimal channel length for a TFT incorporating an interfacial layer of gold clusters. As the channel length decreases, the probability for the presence of continuous, conductive paths through the deposited ultra-thin gold layer from source to drain electrode increases. If the channel length is short enough, then the TFT may have higher leakage current that results in low ON/OFF current ratio.
Examples 5 and 6 relate to TFTs having SWCNTs dispersed in the semiconductor matrix. These examples have a common type of substrate: 1,000 Å SiO2/p-Si/Al. Boron doped p-Si, having a bulk resistivity of about 5 to 30 ohm-cm, together with about 5,000 Å of aluminum on the back side, serves as the gate electrode for TFTs. TIPS pentacene 1 wt % was dissolved in dichlorobenzene (DCB), together with 2.5 wt % of polystyrene as the basic active layer solution. The active layers for TFTs were formed using a mixture that contained 0.01 wt % SWCNTs/0.9 wt % TIPS pentacene/2.24 wt % PS in DCB which was coated on the above mentioned substrate using a knife coater.
Example 5 relates to TFTs with SWCNTs blended into organic semiconductor as the active layer on SiO2.
SWCNTs were purchased from Carbon Nanotechnologies Incorporated (Houston, Tex.) with partial purification. Further purification processes were conducted to achieve more purified SWCNTs and to promote dispersion into DCB. The purification processes were as follows:
Single wall carbon nanotube (1.609 g) was suspended in nitric acid (3M, 60 mL). The suspension was refluxed at 120° C. for 4 hours. After the suspension was cooled to room temperature, SWCNTs were collected by filtration and washing with DI water until neutral. The solid was dried at 80° C. overnight and was further heated at 480° C. for 30 minutes in air. 0.961 g of black solid of SWCNTs was left after the high temperature heating to burn off amorphous carbon. The black solid of SWCNTs were then refluxed in HNO3 (3M, 60 mL) at 120° C. for 1 hour. After being cooled to room temperature, solid was collected by filtration and washing with DI water until neutral. 0.959 g of solid was thus obtained after further drying.
0.1 wt % of these purified SWCNTs was then prepared in DCB. The solution was ultrasonically agitated for a few days before blending it with the basic active layer solution to get 0.01 wt % SWCNTs/0.9 wt % TIPS pentacene/2.24 wt % PS in DCB for forming the modified active layer.
A fabrication issue was encountered when the above solution containing even a small fraction of SWCNTs was knife-coated on SiO2 or HMDS treated SiO2 surface. Very poor wetting occurred when knife coating even a small fraction of SWCNTs on an SiO2 or HMDS treated SiO2 surface. Because of the poor wetting, a very low yield of working TFTs was obtained. Of the devices that did work, the performance was poor, as compared to TFTs without the SWCNTs.
In Example 6, TFTs with SWCNTs blended into organic semiconductor as the active layer and were fabricated on metallic clusters which were deposited over the gate dielectric.
The very poor wetting issue of the active solution containing even a small fraction of SWCNTs was overcome by having an ultra-thin layer of metallic cluster deposited on a bare, an HMDS treated SiO2 surface or other polymeric gate insulator surface.
Furthermore, metallic clusters at the interface of the gate insulator and the organic semiconductor contributes additional conducting segments for transporting carriers ballistically.
Therefore, by taking advantage of 3-D and 2-D conducting paths of the SWCNTs in the organic host and metallic clusters at the interface of the gate insulator and semiconductor, respectively, TFTs exhibiting better performance were fabricated.
There is an optimal combination of SWCNTs concentration in the active solution and the density of gold clusters for a given channel length to get a compromise of achieving higher carrier mobility and reasonably high ON/OFF current ratio.
The foregoing description of the various embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. For example, embodiments of the present invention may be implemented in a wide variety of fabrication methods, such as using nanoparticle (gold and others) to form metallic clusters. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US2008/063511 | 5/13/2008 | WO | 00 | 10/16/2009 |
Number | Date | Country | |
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60946780 | Jun 2007 | US |