1. Field of the Invention
The present invention relates to methods of making semiconductor devices using light emitting organic materials, and more specifically, to methods which involve the modification of the properties of an organic film after it has been deposited by either: (i) adding new components into the film from a top or bottom surface; or (ii) by causing components to leave the film from a top or bottom surface.
2. Related Art
Polymers and blends of polymers and small organic molecules have recently been extensively used to fabricate organic light emitting diodes and thin film transistors.
Organic films are typically deposited in thin film form for electrical and optoelectronic applications by uniformly coating a surface by spin-coating or other methods. Sometimes the final organic film itself is not directly formed, but a precursor is deposited which is converted to a polymer by a subsequent step, such as heating or exposure to UV light (e.g. PPV). It is also well known that adding various elements to the organic film can change its electrical and/or optical properties. These may include elements to change the conduction of electrical carriers (e.g. PBD for electron transportability), or dye centers to change the color of photo- and electro-luminescence (e.g. coumarin 6 in PVK). These extra elements are usually added to the original material before the final solid film is deposited. For example, these different groups could be bonded to a polymer chain before the polymer is deposited by spin coating, or may just be added as other polymers or individual smaller molecules to the solution containing the polymer before a thin film is formed. In either case all materials in the original solution become part of the final film.
The goal of fabricating full color flat panel displays has the potential to be reached using organic light emitting diodes (OLEDs). The difficulty with using this technology is that the current deposition techniques, such as spin-coating and evaporation, deposit blanket films. The film can be used to make devices of a single color. To achieve individual emitters of different color next to each other, such as red, green, and blue, the deposited blanket film must be typically etched into a pattern, as might be done by photolithography followed by etching. Then, this process has to be repeated for multiple layers to achieve full color (red, green and blue emitters). Etching of organic films and photoresist processing for lithography on organic films has proven to be technically very difficult and expensive. Therefore, instead of making a blanket film of one color, etching and making a blanket film of another color, it would be beneficial to make one blanket film and later locally change the properties of the film to emit different light colors. Thus, the need for etching would be removed.
Another approach is ink-jet printing local regions, but a problem associated with ink-jetting printing is that the dots printed do not have a uniform thickness.
Accordingly, what is desired, and has not heretofore been developed, is a method to modify the properties of a film after it has been formed, by introducing therein or removing impurities to modify the properties therefrom.
An object of the present invention is to provide a method for manufacturing optoelectronic organic films having locally modified areas.
Another object of the present invention is to provide an organic film with various regions of modified optoelectronic properties.
Still another object and advantage of the invention is to form an organic film with modified properties by applying dopants in desired places.
A further object and advantage of the invention is the provision of a method for forming an organic film with local modified areas by adding impurities to or removing impurities from the film.
Even another object of the invention is to provide a method for locally modifying properties of an organic film without the need for photolithography and etching of the organic film.
A still further object and advantage of the invention is the provision of a method for manufacturing a locally modified organic film with the need for contacting the surface of said film with solvents.
Even an additional object of the invention is to provide a process of forming a locally modified organic film wherein dopant is added to the film in an annealing process.
Yet an additional object of the present invention is to provide a process for transferring a dopant from one layer to another layer.
A further object of this invention is the provision of a process for transferring a dopant from one layer to another layer in a desired pattern.
The methods of this invention involve modification of the properties of an organic film after it has been deposited by either adding new components into it from its top or bottom surface, or by causing components to leave the film from its top or bottom surface. In the examples of these methods, the emitting color of light-emitting diodes are modified based on doped polymers by locally introducing dopants causing different color emission into the film by local application of a solution containing the desired dopant to the film surface (by ink jet printing, screen printing, local droplet application, etc.). This overcomes difficulties encountered with the direct patterning of three separately formed organic layers (each which uniformly coats an entire surface when formed) into regions for separate R, G, and B devices due to the sensitivities of the organic materials to chemicals typically used with conventional patterning technologies. Alternatively, dopants may be introduced in an organic film by diffusion from one layer into the film in local regions or by locally applying them directly into the organic film. Alternatively, dopants may be selectively removed from a film with solvents, etc.
Typically all of the active components are incorporated into the polymer when the polymer film is first formed, for example by spin coating it over a surface. In the present invention, the properties of the material are modified after a solid film has been formed by later introducing new species into the film from either its top or bottom surface, or removing impurities out through the top or bottom surface especially in a patterned arrangement. The method is especially attractive for the local modification of the photoluminescence and/or electroluminesence color of a thin film of the material, for example to create red, green, and blue light-emitting regions after a surface has been coated with a thin film of the material which is the same everywhere.
Other important objects and features of the invention will be apparent from the following Detailed Description of the Invention taken in connection with the accompanying drawings in which:
a and 1b are diagrams of the application of dye on top of PVK film.
a and 2b are diagrams of dye on PVK film under UV illumination.
a is a diagram of a device and
a and 5b are diagrams of removal of local dye with acetone.
a is a diagram of a device and
a is an experiment showing the effects of temperature on devices fabricated in accordance with the invention, and
a–10c illustrate the steps in introducing film dopants from the top.
a–11c illustrate the steps in introducing dopants from the bottom.
a–12c illustrates the steps for spatially modifying properties of polymer film.
a–13b illustrate the spectra of PVK and PVK with C6.
a–14c illustrate the steps in removing dopant from a polymer film into the underlying layer.
a–15c illustrate the steps in forming patterned addition of dopant from the top.
a–16c illustrate the steps in fabrication of patterned OLEDs.
a–17d illustrate the steps in fabrication of a passive matrix.
a–18c illustrate the steps in removal of dopant from polymer film in a pattern to the underlying layer.
a–19b illustrate the steps in removal of dopant from the top of a film.
a–20c illustrate the steps in the patterned removal of dopant from the top of a film.
a–21d illustrate the steps in fabrication of an active matrix OLED display.
The goal of fabricating full color flat panel displays has the potential to be reached using organic light emitting diodes (OLEDs). The difficulty with using this technology is that the current deposition techniques, such as spin-coating and evaporation, deposit blanket films. The film can be used to make devices of a single color. To achieve individual emitters of different color next to each other, such as red, green, and blue, the deposited blanket film must be typically etched into a pattern, as might be done by photolithography followed by etching. Then, this process has to be repeated for multiple layers to achieve full color (red, green and blue emitters). Etching of organic films and photoresist processing for lithography on organic films has proven to be technically very difficult and expensive. Therefore, instead of making a blanket film of one color, etching and making a blanket film of another color, it would be beneficial to make one blanket film and later locally change the properties of the film to emit different light colors. Thus, the need for etching would be removed.
The present invention, in a broad, general sense, relates to the application of an organic film and thereafter modifying local characteristics thereof by adding or removing components, i.e. dopants, dyes, etc., to or from the film to change the local characteristics of the film. Specifically, the invention relates to modifying the optoelectronic properties of an organic film by impurity or additional removal in a patterned fashion after application of the film. Even more specifically, the invention relates to modifying the emitting color of light-emitting diodes based on doped polymers by locally introducing dopants causing different color emission into an organic film by local application of solutions containing desired dopants to the film surface, i.e. by ink-jetting or screen printing. Alternatively, impurities contained within the film prior to application can be removed therefrom in desired patterns through various methods such as by application of solvents.
One way for achieving this result is to locally dye a poly(9-vinylcabazole) (PVK a hole transporting polymer) spun-on film, with green, red and blue dyes. The dyes would dissolve in acetone or trichloroethylene (TCE), solvents that do not dissolve PVK, and could be patterned on top of the PVK film using an ink-jet printer. As shown in
To verify this technique, droplets of coumarin 6 (C6, a green dye) dissolved in TCE and Acetone were placed onto a spun-on 1000 angstrom thick PVK film using a pipette and the solvents were given time to evaporate.
In order to state the above observations in a more quantitative way, a photoluminescence spectra was taken.
a shows the device structure, and
In order to further investigate this locally dyeing phenomenon, an experiment was set up to see if dye could be washed out of a blend film, which had been dyed in solution.
a shows a schematic of the device made on the washed film. The film was prepared as mentioned above, and then metal cathodes were evaporated in the washed areas and in the non-washed areas. These cathodes were thermally evaporated and were patterned by a shadow mask.
Thus, devices can be made by locally dyeing a PVK film, or by locally washing a dyed PVK film. Therefore, the next step is to pattern the dye using an ink-jet printer.
An experiment was done to determine if the diameter of the printed spots could be influenced by temperature.
In conclusion, PVK can be locally dyed by dissolving dye in acetone or TCE and dropping it on to the surface. Also, this dyed area can be made into a device. A blend film of PVK and C6 can have the C6 locally washed out of it using acetone, and a device can be made using this technique. At the present time ink-jet printed dyed lines can be made with widths of ˜500 μm. This width can be further reduced by printing with TCE onto a heated substrate to obtain a spot 1/10 of the diameter of a spot made at room temperature. This substrate would have to then be heated again to thermally diffuse the dye into the film.
a–10c illustrate the basic method for introducing film dopants from the top in the fabrication of red, green and blue OLED devices on a common substrate. As shown in
a–11c show the introduction of dopants into a film from the bottom thereof. In
a–12c show the steps of a method for spatially modifying the properties of the polymer film.
This has been demonstrated using dyes C6 (green), C47 (blue), and nile red (green) in acetone solution separately applied to individual regions of a single PVK film, where acetone solution is locally applied by an eyedropper or similar device. Acetone does not cause removal of PVK film, but after evaporation of acetone in a few seconds the fluorescence color of the film under UV excitation has changed.
As illustrated in
The dopant need not be pure dopant, but may be co-deposited with another material. Subsequent process (or the very deposition process itself) can then cause dopant to move into underlying layer. Other material may be removed or remove itself (evaporate), or stay behind as separate layer and be part of final structure doped or undoped.
The spatial variations of
a–14c illustrate the steps in the removal of dopant from polymer film into an underlying layer. In
a–15c shown the patterned addition of dopant from the top with an impermeable barrier. In
a–16c illustrate the application of the method described in
a–17d illustrate the application of the method described in
a–18c illustrate the removal of dopant from polymer film in a pattern to the underlying layer. In
a–19b shows the removal of dopant from the top of an unpatterned film. In
a–20c illustrate the patterned removal of dopant from the top of the film. In
a–21d show the formation of an active matrix OLED display. In
The methods described in this invention may be applied to any organic film, not just polymer based. Solvent methods may cause problems with small organic molecule based films, however, dopants could be deposited by diffusion by thermal treatment by other localized methods such as evaporation through a mask, etc.
It should be further understood that “undoped” means not doped with the dopant being added or removed. Other dopants may be present.
Having thus described the invention in detail, it is to be understood that the foregoing description is not intended to limit the spirit and scope thereof. What is desired to be protected by Letters Patent is set forth in the appended claims.
This application is a national application under 35 U.S.C. § 371 based upon PCT/US99/07970, which was filed on Apr. 12, 1999, and claims priority to provisional application 60/081,492, filed on Apr. 13, 1998.
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/US99/07970 | 4/12/1999 | WO | 00 | 2/1/2001 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO99/53529 | 10/21/1999 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
3614225 | Dinella et al. | Oct 1971 | A |
3615943 | Genser | Oct 1971 | A |
3986823 | Mayer | Oct 1976 | A |
4104091 | Evans, Jr. et al. | Aug 1978 | A |
4218362 | Honjo et al. | Aug 1980 | A |
4243694 | Mansukhani | Jan 1981 | A |
4251285 | Yoldas et al. | Feb 1981 | A |
4332879 | Pastor et al. | Jun 1982 | A |
4736704 | Henninger | Apr 1988 | A |
4833123 | Hashimoto et al. | May 1989 | A |
4914451 | Morris et al. | Apr 1990 | A |
4929666 | Schmidt et al. | May 1990 | A |
4971858 | Yamano et al. | Nov 1990 | A |
5004956 | Kun et al. | Apr 1991 | A |
5006624 | Schmidt et al. | Apr 1991 | A |
5055444 | Kaszczuk | Oct 1991 | A |
5116781 | Agostinelli et al. | May 1992 | A |
5132248 | Drummond et al. | Jul 1992 | A |
5250439 | Musho et al. | Oct 1993 | A |
5312654 | Arimatsu et al. | May 1994 | A |
5385848 | Grimmer | Jan 1995 | A |
5398051 | Fukui et al. | Mar 1995 | A |
5422230 | Boggs et al. | Jun 1995 | A |
5495250 | Ghaem et al. | Feb 1996 | A |
5521047 | Yuh et al. | May 1996 | A |
5538548 | Yamazaki | Jul 1996 | A |
5551973 | Oliver et al. | Sep 1996 | A |
5583349 | Norman et al. | Dec 1996 | A |
5596208 | Dodabalapur et al. | Jan 1997 | A |
5609943 | DeKoven et al. | Mar 1997 | A |
5640180 | Hale et al. | Jun 1997 | A |
5643356 | Nohr et al. | Jul 1997 | A |
5673077 | Kawakami et al. | Sep 1997 | A |
5681756 | Norman et al. | Oct 1997 | A |
5688551 | Littman et al. | Nov 1997 | A |
5693962 | Shi et al. | Dec 1997 | A |
5719467 | Antoniadis et al. | Feb 1998 | A |
5739545 | Guha et al. | Apr 1998 | A |
5777707 | Masaki et al. | Jul 1998 | A |
5801884 | Sato et al. | Sep 1998 | A |
5866922 | Huang et al. | Feb 1999 | A |
5880176 | Kamoto et al. | Mar 1999 | A |
5895692 | Shirasaki et al. | Apr 1999 | A |
5919532 | Sato et al. | Jul 1999 | A |
5953587 | Forrest et al. | Sep 1999 | A |
5972052 | Kobayashi et al. | Oct 1999 | A |
5972457 | Matsuishi et al. | Oct 1999 | A |
6013982 | Thompson et al. | Jan 2000 | A |
6054223 | Tsuchiya et al. | Apr 2000 | A |
6066357 | Tang et al. | May 2000 | A |
6087196 | Sturm et al. | Jul 2000 | A |
6099746 | Kim | Aug 2000 | A |
6150042 | Tamano et al. | Nov 2000 | A |
6329111 | Nojiri et al. | Dec 2001 | B1 |
6575800 | Kobayashi et al. | Jun 2003 | B1 |
20020041926 | Miyashita et al. | Apr 2002 | A1 |
Number | Date | Country |
---|---|---|
2 330 451 | Apr 1999 | GB |
61-36276 | Feb 1986 | JP |
8-165448 | Jun 1996 | JP |
10-12377 | Jan 1998 | JP |
9828946 | Jul 1998 | WO |
WO9912396 | Mar 1999 | WO |
Number | Date | Country | |
---|---|---|---|
60081492 | Apr 1998 | US |