JP2001521269A - Method of manufacturing organic semiconductor device using inkjet printing technology, and apparatus and system using the same - Google Patents

Abstract

(57) Abstract A light emitting system for forming an image is disclosed. The light emitting system of the present invention typically includes a first electrode (90) deposited on a substrate so as to be in contact therewith. Then, one or more conjugated organic buffer layers (40) are deposited so as to be in contact with the first electrode, and then the second electrode (22) is deposited on the conjugated organic buffer layer. The conjugated organic buffer layer (40) controls a current flowing between the first electrode (90) and the second electrode (22). Before or after depositing the respective conjugated organic buffer layer (40), but before depositing the second electrode (22), the conjugated organic deposit (34, 36, 38) may be combined with at least one conjugated organic buffer layer. Ink-jet printing to make contact. The conjugated organic deposit (34, 36, 38) serves to emit an indication when a voltage stimulus is applied to the first electrode (90) and the second electrode (22). Depending on the material of the conjugated organic deposit (34, 36, 38), the display can be luminescent, fluorescent, conductive, etc. A voltage source is used to selectively apply a voltage stimulus to the first electrode (90) and the second electrode (22).

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention generally relates to organic semiconductor devices, and in a specific embodiment, relates to a method of manufacturing an organic semiconductor device using an inkjet printing technique, and an apparatus and a system to which the method is applied.

BACKGROUND OF THE INVENTION [0002] Inorganic semiconductors such as silicon are often used in the fabrication of today's semiconductor photonics devices. Processing such inorganic semiconductor devices can be complex and expensive, and typically includes a crystal growth step, a wafer slicing and polishing step, a step of forming integrated electronic circuits on the wafer, and the like. By comparison, conventional polymers (sometimes called plastics) are relatively easy to process. For example, the manufacture of conventional plastic parts involves relatively simple steps, such as injecting molten plastic material into a mold. Conventional polymers are also flexible and lightweight, and can be manufactured on large areas. However, conventional plastics do not have semiconductor properties and are not suitable for manufacturing semiconductor devices.

[0003] Conjugated polymers are organic materials that combine the electrical and optical properties of semiconductors with the workability of conventional plastics. The semiconducting properties of conjugated polymers include poly (phenylenevinylene), polythiophene (PT), and poly (2-methoxy-5).
Derived from delocalized π orbitals formed in carbon containing compounds such as -2'-ethyl-hexyloxy) -1,4-phenylenepyrylene (MEH-PPV).
Unlike conventional polymers, conjugated polymers have semiconducting properties rather than insulating properties because they have double bonds. Conjugated polymers are low in processing costs, flexible and lightweight, and combine the mass productivity of conventional polymers with the general semiconducting properties of silicon.

[0004] Conjugated polymer devices are typically manufactured by spin coating. Spin coating utilizes the solution processability of polymers. That is, the substrate containing large water droplets of the liquid conjugate polymer is rotated at a high speed around an axis to cause the liquid conjugate polymer to flow outward and coat the substrate with a thin film of the material. However, spin coating has the following disadvantages. That is, spin coating is a waste of solution because most of the liquid conjugated polymer is scattered without covering the surface. Furthermore, spin coating is susceptible to dust and other defects present on the substrate surface. This is because when the liquid organic material is applied onto the substrate surface, any bumps will form a shadow, leaving behind a relatively thin radial trace of the organic material behind the defect.

[0005] Because the flow of the liquid conjugated polymer is poorly controlled, it is not possible to form the desired pattern during spin coating. For this reason, there is a limit to the practical use of conjugated polymers. For example, a light emitting conjugated polymer sandwiched between two electrodes may be used in the manufacture of a light emitting diode (LED) or a light emitting logo (LEL), but a single layer of the conjugated polymer formed by spin coating. Since the pattern is not patterned, the color of the device is limited to a single color, and the electrodes need to be patterned. Also, photolithography techniques, which can be normally used to create patterned electrodes, cannot be used to pattern conjugated polymer layers. This is because the double bond of the conjugated organic substance may be broken by the photolithography technique.

[0006] Another type of organic semiconductor material is conjugated small organic molecules. In the present invention, a conjugated organic compound (organic substance) is defined as meaning a polymer (an organic substance having more than two repeating units per molecular chain) and a small organic molecule (an organic substance composed of a single molecule). Small organic molecules have the same (electrical and optical) properties as conjugated polymers, but utilize slightly different processing techniques. Organic molecules are usually processed using thermal sublimation in an ultra-high vacuum environment to form a desired thin film. The thickness of the thin film is typically about 100 nm. Organic molecules often utilize the same device structure as conjugated polymers, ie, an organic thin film sandwiched between two electrodes.
Patterning of the organic thin film can be performed using a shadow mask, but this method is time consuming and expensive because the shadow mask must be accurately aligned. Further, the horizontal resolution is also limited. Organic molecules can be processed by conventional spin coating methods, but they cannot be patterned by this method. Organic molecules are typically processed by being mixed with a host conjugated polymer, and the resulting mixture obtains the mechanical properties of the polymer that are advantageous for thin film formation. FIG. 3 shows an example of a typical organic compound of a buffer layer and an ink-jet printed deposit.
1, FIG. 32 and FIG.

High resolution patterned conjugated organic materials can also be deposited using inkjet printing (IJP) technology, a common technique in desktop publishing. The application of inkjet printing techniques to the deposition of patterned conjugated organics is described in TR Hebner et al., “Organic Light Emitting Devices,” published in Applied Physics Letters, Vol. 72, p. 519 (1998). Ink-jet printing of doped polymers for o
rganic light emitting devices). This document is cited in this application as a reference. However, conventional inkjet printing technology prints a low-concentration dye-containing polymer solution, resulting in a poor film that is unsuitable for high-quality semiconductor devices.

Even if an appropriate pattern of a conjugated organic substance can be deposited on the lower electrode, a problem still remains. Since dots are formed in the inkjet printing, an organic film printed using the inkjet printing may have pinholes. When the upper electrode material is deposited on the patterned conjugated organic thin film, the upper electrode material may come into contact with the lower electrode via a pinhole, resulting in a short circuit and making the device unusable.

SUMMARY OF THE DISCLOSURE It is an object of embodiments of the present invention to provide a method of manufacturing an organic semiconductor device using hybrid inkjet printing technology, and a system and apparatus using the same. This method is relatively resistant to defects on the substrate surface, and has the electrical and optical properties of conventional semiconductors and the low cost processability, flexibility, light weight, and mass productivity of conventional organics. Are combined.

It is another object of an embodiment of the present invention to provide a method of manufacturing an organic semiconductor device using hybrid inkjet printing technology, and a system and an apparatus using the same. In accordance with this method, it is possible to form luminescent displays, devices, logos, and grayscale images having independent luminescent areas in single or multiple colors that are accurately patterned.

It is still another object of embodiments of the present invention to provide a method of manufacturing an organic semiconductor device using hybrid inkjet printing technology, and a system and an apparatus using the same. According to this method, a high-quality shadow mask for manufacturing a semiconductor device, a biosensor, a photovoltaic device, and a photoelectric detector can be formed.

[0012] These and other objects are achieved by a lighting system for forming an image. Such light emitting systems typically have a first electrode deposited in contact on a substrate. Thereafter, one or more conjugated organic buffer layers are deposited in contact with the first electrode, and then a second electrode is deposited on the conjugated organic buffer layer. The conjugated organic buffer layer controls the flow of current between the first and second electrodes. Before or after depositing each conjugated organic buffer layer, but after depositing the second electrode, the conjugated organic deposit is inkjet printed into contact with at least one conjugated organic buffer layer.

The conjugated organic deposit serves to provide an indication when a voltage stimulus is applied to the first and second electrodes. Depending on the material of the conjugated organic deposit, the indication may be light emission, fluorescence, conductivity, or the like. A voltage source is used to selectively apply a voltage stimulus to the first and second electrodes.

The above and other objects, features, and advantages of embodiments of the present invention will become apparent to those skilled in the art from a reading of the following description of embodiments of the invention, taken in conjunction with the accompanying drawings and claims.

(Detailed description of preferred embodiments) [0015] In the following, embodiments will be described with reference to the accompanying drawings. The accompanying drawings form a part of the embodiments and illustrate specific embodiments for practicing the invention. It will be apparent to one skilled in the art that other embodiments may be utilized and modifications may be made without departing from the scope of the preferred embodiments of the present invention.

The conjugated organic material has the low-cost processability, flexibility, light weight, and mass productivity of the conventional organic material and the general semiconductor properties of an inorganic semiconductor. FIG.
1 shows a conjugated organic semiconductor device 10 according to an embodiment of the present invention. In the conjugated organic semiconductor device 10, a first electrode 14 made of a metal or a metal oxide is formed on a substrate 12 by a conventional deposition technique. The substrate 12 is made of a solid material such as glass, plastic, a semiconductor wafer, and a metal plate, and has an insulating thin film provided thereon, or is made of a soft material such as plastic and metal foil, and has an insulating thin film formed thereon. Is provided. In a preferred embodiment, first electrode 14 comprises indium tin oxide (ITO). On the first electrode 14, a thickness of about 1 to 1000
A substantially uniform nm conjugated organic buffer layer 16 is formed by spin coating, thermal sublimation or other conventional application methods. On the conjugated organic buffer layer 16,
At least one conjugated organic deposit 20 using an inkjet printhead 18
Is printed. The reason for using inkjet printing is that, unlike spin coating, inkjet printing can print a conjugated organic deposit 20 having a fine resolution, and the conjugated organic deposit 20 is horizontal to the conjugated organic buffer layer 16. This is because the material is jetted vertically instead of flowing into the substrate, so that it is relatively resistant to dust and defects existing in the substrate, and that no material is wasted in the coating process.

As shown in FIG. 2, a second electrode 22 is deposited on the conjugated organic deposit 20 and the conjugated organic buffer layer 16 using conventional metal deposition techniques. Conjugated organic buffer layer 1
6 has sufficient insulating properties, so that a short circuit does not occur between the second electrode 22 and the first electrode 14.

In another embodiment of the present invention, shown in FIG. 4, the conjugated organic deposit 20 is deposited directly on the first electrode 14 using inkjet printing. Thereafter, the conjugated organic buffer layer 16 is formed on the conjugated organic deposit 20 and the first electrode 14 by spin coating or other conventional coating method. Thereafter, a second electrode 22 is deposited on the conjugated organic buffer layer 16 using conventional metal deposition techniques.

In yet another embodiment, shown in FIGS. 6 and 8, a plurality of conjugated organic buffer layers 16 and a plurality of layers of conjugated organic deposits are formed in a semiconductor device in a longitudinal or third dimension. And the functional density is improved.

FIGS. 2, 4, 6 and 8 illustrate a single first electrode 14 and a single second electrode 22
Although FIG. 3, FIG. 5, FIG. 7, FIG. 9 and FIG. 10 show other embodiments of the present invention, a plurality of first electrodes 14 and second electrodes 22 are respectively provided. It may be deposited on the conjugated organic deposit 20. Although not shown in FIGS. 3, 5, 7, 9, and 10, the plurality of first electrodes 14 are formed laterally with respect to the plurality of second electrodes 22 (see FIGS. 3 and 5). 5, see FIGS. 7, 9 and 10).

In the embodiment shown in FIG. 10, a plurality of first electrodes 14 (not shown) are inkjet printed on substrate 12. Thereafter, the conjugated organic buffer layer 16 is applied to the plurality of first electrodes 14 by spin coating or other conventional coating method.
Form on top. Then, a plurality of second electrodes 22 are inkjet printed on the conjugated organic buffer layer 16.

In another embodiment of the present invention, shown in FIGS. 11 and 12, only one conjugated organic deposit 20 is shown for purposes of illustration. The conjugated organic deposit 20 comprises a conductive or charge transfer organic material. Since the conductive / charge transfer conjugate organic deposit 20 has better charge injection characteristics than the electrode material, when a voltage is applied to the second electrode 22 and the first electrode 14, the current 24
Flows between the second electrode 22 and the first electrode 14 only to the conjugated organic buffer layer 16 on which the conductive / charge transfer conjugated organic deposit is printed.

Among various organic semiconductor devices, an electroluminescent (EL) device is particularly noteworthy. This includes light sources, single or multicolor displays, luminescent logos,
This is because it may have future applications in multicolor light emitting devices, greeting cards, and low and high density guided displays. Thus, in yet another embodiment, the first electrode 14 and the substrate 12 are transparent and the conjugated organic buffer layer 1
6 is made of a light emitting material. In such an embodiment, light emission 32 is generated from conjugated organic semiconductor device 10 by current 24 flowing through conjugated organic buffer layer 16.

In another embodiment of the present invention, shown in FIGS. 13 and 14, only one conjugated organic deposit 20 is shown for explanation. The conjugated organic deposit 20 and the conjugated organic buffer layer 16 are made of a light emitting organic material, and the first electrode 14 and the substrate 12 are transparent. When a sufficiently high voltage is applied to the second electrode 22 and the first electrode, the second electrode 2
A current 24 flows through the conjugated organic buffer layer 16 between the second electrode 1 and the first electrode 14. In the portion where the conjugated organic deposit 20 is not present, the color emitted by the conjugated organic buffer layer 16 (see reference numeral 26) depends on the composition of the conjugated organic buffer layer 16. Where the conjugated organic deposit 20 is present, the color of the emission depends on where the electrons and holes recombine. Generally, if the conjugated organic deposit 20 is sufficiently thick, the electrons and holes recombine within the conjugated organic deposit 20 and the color of the emission (see reference numeral 32) will be the composition of the conjugated organic deposit 20. Depends on If the conjugated organic deposit 20 is sufficiently thin, the electrons and holes recombine in the conjugated organic buffer layer 16 and the color of the emitted light depends on the composition of the conjugated organic buffer layer 16. However, if the thickness of the conjugated organic deposit 20 is substantially the same as that of the conjugated organic buffer layer 16, the electrons recombine near the boundary between the conjugated organic deposit 20 and the conjugated organic buffer layer 16. Sediment 20
And the color of the conjugated organic buffer layer 16.

In another embodiment of the present invention shown in FIG. 15, only one conjugated organic deposit 20 is shown for explanation. The conjugated organic deposit 20 is made of a conjugated organic material that can partially diffuse into the conjugated organic buffer layer 16. The conjugated organic buffer layer 16 is made of poly-9-
Consisting of vinylcarbazole (PVK) or polyfluorene (PF) or other similar compounds, the conjugated organic deposit 20 comprises soluble poly (p-phenylenevinylene) (PPV), MEH-PPV, organic dyes, polyfluorene derivatives, Or consists of other similar compounds. In such an embodiment, a small amount of the conductive conjugated organic deposit 20 diffuses into the conjugated organic buffer layer 16 (see reference numeral 30),
It acts as a charge transfer dopant in the conjugated organic buffer layer 16. The diffusion of the guest dopant (conjugated organic organism 20) into the host buffer layer (conjugated organic buffer layer 16) depends on the material properties of the host and guest material and the solvent compatibility (polar or non-polar) of the host and guest material. Action. When a voltage is applied to the second electrode 22 and the first electrode 14, the energy transfer from the host to the guest in the region of the conductive conjugated organic deposit 20 is facilitated, and the connection between the second electrode 22 and the first electrode A small amount of dopant may be required to pass the current 24 therebetween.

In yet another embodiment, the conjugated organic buffer layer 16 and the conjugated organic deposition material that can partially diffuse into the conjugated organic buffer layer 16 are luminescent;
The first electrode 14 and the substrate are transparent. When the current 24 flows through the conjugated organic buffer layer 16, the portion where the conjugated organic deposit 20 partially diffuses into the conjugated organic buffer layer 16 (see reference numeral 30) becomes the conjugated organic deposit 20 and the conjugated organic deposit 20. Light is emitted in a color depending on the band gap and energy level of the material constituting the organic buffer layer 16. In general, if the band gap of the conjugated organic deposition material is smaller than the conjugated organic buffer layer and the energy level is lower than the conjugated organic buffer layer, the color of the emission (see reference numeral 28) will be Depends on composition. Otherwise, the color of the emission depends on the composition of the conjugated organic buffer layer 16.

As shown in FIGS. 3, 5, 7, 9, and 10, a plurality of first and second electrodes (14) are formed on each conjugated organic deposit 20 using inkjet printing.
And 22) can also be formed. As shown in FIG. 16, to form the plurality of second electrodes of FIG. 3, first, an organic mask 72 is deposited on the conjugated organic buffer layer 16 by inkjet printing. Next, a second electrode material 74 is deposited on the organic mask 72 and the conjugated organic buffer layer 16 by spin coating or other conventional coating methods. As a material for forming the second electrode material 74 and the organic mask 72, a material for the second electrode material 74 to be firmly adhered to the conjugated organic buffer layer 16 is selected. Select one that does not adhere very much to Then adhesive sheet 7 such as adhesive tape
6 is pressed firmly against the second electrode member 74. Then, when the adhesive sheet 76 is removed, as shown in FIG. 17, since the second electrode member 74 and the organic mask 72 have different adhesive characteristics, a part of the organic mask 72 and the second electrode member 74 together with the adhesive sheet 76 are removed. Removed. The remaining second electrode material 74 forms a plurality of second electrodes. Multiple second
This method of forming an electrode involves the first electrode 14 shown in FIGS. 5, 7, 9 and 10.
And the second electrode 22.

In an embodiment of the present invention, the order of micron-sized organic light emitting diodes
regular) provides a way to form an array. In this method, the size of the light emitting diode is limited only by the nozzle size of the inkjet print head.
One of the applications of regular arrays of conjugated organic light emitting diodes is in multicolor light emitting displays such as television screens and computer monitors. In such applications, red, green, and blue dots are used to form a color image. As shown in FIG. 18, several different emission diffusion conjugated organic deposits 34, 36, and 38 having band gaps and energy levels corresponding to red, green, and blue, respectively, are provided with band gaps and energy levels corresponding to blue. And deposited on the conjugated organic buffer layer 40. The light-emitting diffusion conjugated organic deposits 34, 36, and 38 partially diffuse into the buffer layer 40, and when a voltage is applied to the second electrode 22 and the first electrode, the light-emitting diffusion conjugated organic deposits 34, 36, And buffer layer 40 below 38
The emission spectrum of the buffer layer 40 is changed so that the buffer layer 40 emits red 42, green 44, and blue 46. By selectively applying a voltage between the second electrode 22 and the first electrode 14, the red, green, and blue light emitting diodes can be turned on and off, and a simple matrix multicolor light emitting display can be obtained. Can be

In another embodiment shown in FIG. 19, an active matrix multi-color luminescent display is shown. A plurality of gate electrodes 92 are deposited on substrate 12 by ink jet printing or other conventionally used deposition techniques. The transistor 48 including the insulating material 50, the source electrode 90, and the drain electrode 88 is formed over the plurality of gate electrodes 92. Next, a conjugated organic buffer layer 40 is deposited on the transistor by spin coating or other conventional coating method, leaving the conjugated organic buffer layer 40 in contact with the drain electrode 88. Then, the emission diffusion conjugate organic deposits 34, 36 and 38 are inkjet printed on the conjugate organic buffer layer 40. Finally, a single second electrode 22 is deposited on the emission diffusion conjugated organic deposits 34, 36 and 38. Source electrode 90, transistor 48, conjugate buffer layer 4
0, the current flowing through the conjugated organic deposit 34, 36 or 38 and the second electrode 22,
The light emission of the diffusion conjugated organic buffer layer 40 is controlled by the voltage at the gate terminal 52. FIG. 19 is provided for illustrative purposes only, and other conventional methods of fabricating a transistor-based active matrix multicolor emissive display may be used in embodiments of the present invention.

Generally, luminescent materials with higher band gaps and higher energy levels (eg, FIG. 1)
8), the bandgap and energy levels (eg, red, green, blue) of the organic deposit shown in FIG. 18 are doped with the same or lower luminescent material. Emits a lower bandgap and lower energy level color when a bias voltage is applied, hi a preferred embodiment, less than about 25 percent of the doping material diffuses into the buffer layer 40 to achieve such a color change. Figure 20 shows different concentrations of MEH-PPP.
When poly (para-phenylene) (PPP) is introduced into a polymer system,
This indicates whether the light emission color of the light emitting diode changes. FIG. 21 shows MEH-P
This shows that the current-voltage (IV) characteristics are the same regardless of the concentration of PP.

In yet another embodiment, shown in FIGS. 22 and 23, a silicon oxide (SiO ₂ ) or polymer partition on which a pre-patterned lateral electrode 56 is provided on a printed transparent substrate 12 Is used to produce an array of red, green and blue light emitting diodes. The conjugated organic buffer layer 1 is formed by the silicon oxide partition 54.
6, and red, green, blue conductive / charge transfer polymers 34, 36, 38 can be inkjet printed directly on the lateral electrodes 56. The SiO ₂ partition 54 also serves as a shadow mask when depositing the second electrode 22.

Other uses for the light emitting conjugated organic semiconductor device 10 include organic light emitting logos and monochromatic or multicolor emitting devices. In this case, the inkjet printing is controlled to print a pattern of the conductive / charge transfer conjugated organic material. Unlike multicolor displays, in which the color pattern is constantly changing as seen by the eye, luminescent logos and monochromatic or multicolor devices typically have luminescent areas of large dimensions but of fixed color. . To form such a device, a conductive / charge-transfer and / or luminescent organic conjugate organic deposit 20 may be printed directly on the conjugated organic buffer layer 16 (see FIG. 11) or on a transparent first electrode 14. (See FIG. 12). The pattern of the conjugated organic deposit 20 defines the light emitting area. By applying a voltage between the second electrode 22 and the first electrode 14, a large light-emitting logo can be turned on. Since the current flows through the conjugated organic deposit 20 but is not removed therefrom, the conjugated organic deposit 20 can be provided with a separation portion (a physically isolated pattern). By adjusting the bias voltage, the light-emitting logo can have a high contrast with respect to the background. Also, the brightness of the luminescent logo is a few tenths of a candela (
It can be adjusted over a wide range from cd) / m ² to 100 cd / m ² .

The production of a luminescent logo according to a preferred embodiment of the present invention is shown in FIG. First, a cleaning agent is applied to an indium tin oxide (ITO) electrode 58 deposited on a glass substrate 60.
Normal ultrasonic cleaning is performed while continuously using deionized water (DI), acetone, and alcohol to remove dirt on the surface. Next, the ITO electrode 58 and the glass substrate 60 are baked at a high temperature for about 12 hours. Next, a conductive polymer logo 62 is deposited on the ITO electrode 58 from an aqueous solution of 3,4-polyethylenedioxythiophene-polystyrene sulfonate (PEDOT) by inkjet printing. And
The PEDOT conductive polymer logo 62 is dried in air at about 100 ° C. for about 12 hours. In another embodiment, Adv. Materials, Vol. 9, pp. 475-477 (19)
JA Rogers et al., “Microcontact printing and electroplating on curved substrates, stand-alone three-dimensional metal microstructure (Microcontact printing an)
d electoplating on curved substrates; production of free-standing three-
Other methods may be used, such as the stamping method described in “Dimensional metallic microstructures”. This document is cited in this application as a reference. FIG.
As shown in FIG. 5, MEH-P made from about 1 percent MEH-PPV solution
A PV buffer layer 64 is spin coated on the PEDOT conductive polymer logo 62 at a rate of about 2500 revolutions per minute (RPM) and a calcium (Ca) cathode
Deposited on the H-PPV buffer layer 64. The resulting device has an active cathode area epoxied with aluminum or cover glass 68.
Contain by doing. In the manufacturing method of the present invention, it is also possible to use other materials having properties similar to those described above.

FIG. 26 shows representative luminance-voltage (LV) curves for a device with a PEDOT conductive polymer layer (reference numeral 70) and a device without (reference numeral 78). From this figure, it is understood that the performance is improved by forming the PEDOT conductive polymer layer. For example, when operated the device at 5 volts, the light-emitting diode having a PEDOT conducting polymer layer is about 200 cd / ^{m 2} brightness level. On the other hand, the light emitting diode having no PEDOT conductive polymer layer has a luminance level about three orders of magnitude lower.

In another embodiment of the present invention, a luminescent logo may be used for a particular application to form a grayscale luminescent image. FIG. 27 shows a four-level gray scale 80 defined by the light emitting dot density, and FIG. 28 shows a luminance curve 82 showing a typical relationship between the luminance of the light emitting dots and the density. The gray scale to which the embodiment of the present invention is applied can be rotated almost continuously by changing the dot size or the dot density.

In addition to organic luminescent logos and displays, embodiments of the present invention can be applied to other organic and optoelectronic devices. Examples include, but are not limited to, transistors, photovoltaic cells, artificial nose, physical devices,
Chemical devices, bio devices, and electronic integrated circuits. Examples of physical devices include, but are not limited to, optical sensors (arrays), X-ray detectors (arrays), image sensors (arrays), photoelectric detectors, and photovoltaic devices.
Examples of chemical devices include, but are not limited to, gas sensors (arrays) and moisture (solvent) sensors. Examples of biodevices include, but are not limited to, sensors for detecting blood glucose (glucose) and enzymes. Furthermore, light-emitting diodes can be efficiently manufactured on a semiconductor wafer as a light source used for communication between and inside a chip of a computer, a telecommunication device, and the like by inkjet printing. In embodiments of the present invention, examples of materials that can be used to pattern electronic devices include, but are not limited to, organic conjugated molecules, conjugated polymers, inorganic nanocrystals, organic nanocrystals, dye molecules. , And combinations thereof. The device described above produces an output in the form of light emission, conduction or fluorescence, as already mentioned.

As an example of the embodiment of the present invention, there is an artificial nose using conductive or fluorescent light as display means. As shown in FIG. 29, a plurality of layers of the conjugate organic deposit 20 and the conjugate organic buffer layer 16 are formed on the substrate 12 by the above-described technique. However, before each conjugated organic deposit 20 is inkjet printed, two electrodes 84 are formed and provided on the two electrodes 84. Each conjugated organic deposit 20 is made of a special material whose conductivity changes when the fluid or gas sample 86 diffuses into the conjugated organic buffer layer 16 and the conjugated organic deposit 20. The conductivity of each conjugated organic deposit 20 is sensed by two electrodes within the conjugated organic deposit 20. Multiple conjugated organic deposits 2 provided in each layer
0 is a conductive "" that can be used to identify the chemical composition of the fluid or gas sample 86.
Signal. In yet another embodiment, the plurality of conjugated organic buffer layers 1
6 is made of a special material, each of which functions as a fluid or gas separation membrane. Accordingly, each layer of the conjugated organic deposit 20 is configured to test only a particular type of fluid or gas. This is because other types of fluids or gases are filtered by the plurality of conjugated organic buffer layers 16.

In another embodiment of the present invention, shown in FIG. 30, the plurality of conjugated organic deposits 20 fluoresce under certain conditions. No electrodes are present in the conjugated organic deposit 20. Each of the conjugated organic deposits is made of a special material that changes its fluorescence when a fluid or gas sample 86 diffuses into the conjugated organic buffer layer 16 and the conjugated organic organism 20. The fluorescence of each conjugated organic deposit 20 is represented by illuminating the entire device with ultraviolet light. The plurality of conjugated organic deposits 20 in each layer emit a fluorescent “signal” that can be used to identify the chemical composition of the fluid or gas sample 86. In yet another embodiment, the plurality of conjugated organic buffer layers 16 are made of a special material that functions as a fluid or gas separation membrane. Accordingly, each layer of the conjugated organic deposit 20 is configured to test only a particular type of fluid or gas. This is because other types of fluids or gases are filtered by the plurality of conjugated organic buffer layers 16.

As described above, embodiments of the present invention provide a method of manufacturing an organic semiconductor device by an inkjet printing technique, and a system and an apparatus using the same. This method is relatively resistant to defects on the substrate surface, and has the electrical and optical properties of conventional semiconductors and the low cost processability, flexibility, light weight, and mass productivity of conventional organics. Are combined. Further, in accordance with embodiments of the present invention, it is possible to form light-emitting displays, devices, logos, and grayscale images having independent light-emitting areas in single or multiple colors that are accurately patterned. Further, according to embodiments of the present invention, a high quality shadow mask for manufacturing semiconductor devices, biosensors, photovoltaic devices and photoelectric detectors can be formed.

The embodiments of the present invention described above are for explanation and do not limit the present invention. The scope of the present invention is not intended to be exhaustive or limited by the description of this embodiment, but is to be defined in the appended claims.

[Brief description of the drawings]

FIG. 1 illustrates inkjet printing of a conjugated organic deposit on a conjugated organic buffer layer, according to an embodiment of the present invention.

FIG. 2 comprises a single second electrode and a single first electrode sandwiching a single layer of a conjugated organic deposit printed on a single conjugated organic buffer layer, in accordance with an embodiment of the present invention. FIG. 2 is a view showing a conjugated organic semiconductor device.

FIG. 3 illustrates a plurality of second electrodes and a plurality of first electrodes (shown in FIG. 3) sandwiching a single layer of a conjugated organic deposit printed on a single conjugated organic buffer layer in accordance with an embodiment of the present invention. FIG. 2 is a diagram showing a conjugated organic semiconductor device including (i).

FIG. 4 illustrates a single second electrode and a single first electrode sandwiching a single conjugated organic buffer layer deposited on a single layer of a conjugated organic deposit in accordance with an embodiment of the present invention. Prepare,
It is a figure showing a conjugated organic semiconductor device.

FIG. 5 illustrates a plurality of second electrodes and a plurality of first electrodes (shown in FIG. 5) sandwiching a single conjugated organic buffer layer deposited on a single layer of conjugated organic deposits in accordance with an embodiment of the present invention. FIG. 2 is a diagram showing a conjugated organic semiconductor device including (i).

FIG. 6 comprises a single second electrode and a single first electrode sandwiching multiple layers of conjugated organic deposits printed over multiple conjugated organic buffer layers, according to embodiments of the present invention.
It is a figure showing a conjugated organic semiconductor device.

FIG. 7 illustrates a plurality of second electrodes and a plurality of first electrodes (not shown) sandwiching a plurality of layers of a conjugated organic deposit printed on a plurality of layers of a conjugated organic buffer according to embodiments of the present invention. FIG. 3 is a diagram showing a conjugated organic semiconductor device including ()).

FIG. 8 illustrates a single second electrode and a single first electrode sandwiching a plurality of conjugated organic buffer layers deposited over a plurality of layers of conjugated organic deposits in accordance with an embodiment of the present invention. It is a figure which shows the conjugated organic semiconductor device provided.

FIG. 9 illustrates, according to an embodiment of the present invention, a plurality of second electrodes and a plurality of first electrodes (not shown) sandwiching a plurality of conjugate buffer layers deposited on a plurality of layers of conjugated organic deposits. It is a figure which shows the conjugated organic semiconductor device provided.

FIG. 10 is a diagram showing a conjugated organic semiconductor device including a plurality of second electrodes and a plurality of first electrodes (not shown) sandwiching a single conjugated organic buffer layer according to an embodiment of the present invention. is there.

FIG. 11 shows a single second electrode and a single first electrode sandwiching a single conductive / charge transfer conjugated organic deposit printed on a single conjugated organic buffer layer according to an embodiment of the present invention. It is a figure which shows the conjugated organic semiconductor device provided with.

FIG. 12 shows a single second electrode and a single first electrode sandwiching a single conjugated organic buffer layer deposited on a single conductive / charge transfer conjugated organic deposit, according to an embodiment of the present invention. It is a figure which shows the conjugated organic semiconductor device provided with.

FIG. 13 illustrates a single second electrode and a single first electrode sandwiching a single emission conjugated organic deposit printed on a single emission conjugated organic buffer layer in accordance with an embodiment of the present invention. It is a figure which shows the conjugated organic semiconductor device provided.

FIG. 14 comprises a single second electrode and a single first electrode sandwiching a single emission conjugated organic buffer layer deposited on a single emission conjugated organic deposit, in accordance with an embodiment of the present invention. FIG. 2 is a view showing a conjugated organic semiconductor device.

FIG. 15 shows a single second electrode and a single first electrode sandwiching a single light-emitting diffusion conjugated organic deposit printed on a single light-emitting conjugated organic buffer layer according to an embodiment of the present invention. It is a figure which shows the conjugated organic semiconductor device provided with.

FIG. 16 is a diagram showing that an organic mask, a second electrode material, and an adhesive sheet are deposited when forming a plurality of second electrodes in a conjugated organic semiconductor device according to an embodiment of the present invention.

FIG. 17 is a diagram illustrating removing an adhesive sheet and an organic mask when forming a plurality of second electrodes in a conjugated organic semiconductor device according to an embodiment of the present invention.

FIG. 18 is a diagram illustrating red, green, and blue conjugated organic light emitting diodes in a simple matrix multicolor light emitting display according to an embodiment of the present invention.

FIG. 19 is a diagram illustrating red, green, and blue conjugated organic light emitting diodes and a control transistor in an active matrix multicolor light emitting display according to an embodiment of the present invention.

FIG. 20 is a graph showing how the emission color of a conjugated organic light emitting diode changes when light emitting conjugated organic dopant materials having different concentrations are introduced into a light emitting conjugated organic buffer layer according to an embodiment of the present invention.

FIG. 21 shows that, according to the embodiment of the present invention, the current-voltage (I−) of the conjugated organic light-emitting diode is independent of the concentration of the luminescent conjugated organic dopant material introduced into the conjugated organic buffer layer.
V) Graph showing that the characteristics are the same.

FIG. 22 illustrates the use of a silicon oxide partition to produce a conjugated organic light emitting diode array for a multicolor light emitting display according to an embodiment of the present invention.

FIG. 23 is a side view illustrating the fabrication of a conjugated organic light emitting diode array for a multicolor light emitting display using a silicon oxide partition according to an embodiment of the present invention.

FIG. 24 illustrates the manufacture of a luminescent logo (LEL) according to an embodiment of the present invention.

FIG. 25 is a side view showing the manufacture of the luminescent logo shown in FIG. 24.

FIG. 26 is a graph showing typical luminance-voltage (LV) characteristics of a device with and without a conjugated organic deposit according to an embodiment of the present invention. Is improved.

FIG. 27 is a diagram illustrating a four-level gray scale defined by luminescent dot densities used to form a luminescent image, according to an embodiment of the present invention.

28 is a graph of a luminance curve showing a typical relationship between gray scale luminance and light emitting dot density in FIG. 27.

FIG. 29 illustrates an artificial nose having a conductive display, according to an embodiment of the present invention.

FIG. 30 illustrates an artificial nose having a fluorescent display, according to an embodiment of the present invention.

FIG. 31 illustrates examples of representative organic compounds suitable for buffer layers and inkjet print deposits.

FIG. 32 illustrates examples of representative organic compounds suitable for buffer layers and ink-jet printed deposits.

FIG. 33 shows examples of representative organic compounds suitable for buffer layers and inkjet print deposits.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG , KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Jan, Jan 90049 Los Angeles Bayris Road, California 90049 F-term 3K007 AB04 AB18 BA06 CA01 CB01 DA00 DB03 EB00 FA00 FA01

Claims (28)

[Claims] 1. A semiconductor device that emits a display in response to a stimulus, comprising: a substrate supporting the semiconductor device; at least one first electrode supported by the substrate; and at least one first electrode supported by the substrate. At least one second electrode for flowing current between the at least one first electrode and at least one first electrode and at least one first electrode supported between the at least one first electrode and the at least one second electrode; At least one conjugated organic buffer layer for controlling a current flowing between the two second electrodes, and at least one first electrode and at least one second electrode contacting the at least one conjugated organic buffer layer And at least one ink-jet printed conjugate that forms a display emitted by the semiconductor device when a stimulus is applied. Semiconductor device comprising a sediment. 2. The method according to claim 1, wherein the at least one conjugated organic deposit is made of a conductive material, and the conjugated deposition is applied when a voltage stimulus is applied to at least one first electrode and at least one second electrode. 2. The device according to claim 1, wherein a current flows through the object and at least one conjugated organic buffer layer. 3. The device according to claim 2, wherein the substrate and the at least one first electrode are transparent, and the at least one conjugated organic buffer layer is made of a material capable of emitting light when a current flows. 4. The apparatus according to claim 2, wherein the substrate and the at least one first electrode are transparent, and the at least one conjugated organic deposit comprises a substance capable of emitting light when a current flows. 5. The method of claim 1, wherein the substrate and at least one first electrode are transparent, at least one conjugated organic deposit comprises a luminescent guest material, and at least one conjugated organic buffer layer comprises a luminescent host material. Partially diffuses into the host material, and the bandgap width and energy level of the guest material do not exceed the host material, so that when a voltage stimulus is applied to at least one first electrode and at least one second electrode, Correspondingly, the semiconductor device emits light according to the guest material, so that a current flows between the at least one first electrode and the at least one second electrode via the guest material and the host material. The apparatus of claim 1, wherein: 6. The apparatus comprises a plurality of groups of conjugated organic deposits, each group comprising red,
The device according to claim 5, comprising three conjugated organic deposits containing a guest substance capable of emitting green and blue light. 7. The at least one conjugated organic buffer layer comprises a polyfluorene derivative, the at least one conjugated organic deposit comprises a soluble poly (p-phenylenevinylene) derivative and a polyfluorene derivative, and at least one first electrode comprises The device of claim 5, wherein the device is comprised of indium tin oxide. 8. A semiconductor device that emits a display in response to a stimulus, comprising: a substrate for supporting the semiconductor device; a plurality of source electrodes supported by the substrate for inducing a current flow; A plurality of gate electrodes supported on the substrate and controlling the flow of current, supported between the plurality of source electrodes and the plurality of gate electrodes, a source terminal connected to the source electrode, a gate terminal connected to the gate electrode, And a plurality of transistors each having a drain terminal, the plurality of transistors controlling current flow, the second electrode supported by the plurality of transistors and facilitating the flow of current between the plurality of transistors, and the plurality of transistors and the second electrode Between the drain terminal of the transistor and the second
A conjugated organic buffer layer supported to contact the electrode and controlling the current flowing between the drain terminals of the plurality of transistors and the second electrode; and a conjugated organic buffer layer supported by each transistor and in contact with the conjugated organic buffer layer; An apparatus comprising a plurality of conjugated organic deposits that are ink-jet printed to form a display emitted by a semiconductor device when a stimulus is applied. 9. A semiconductor device that emits a display in response to a stimulus, comprising: a substrate supporting the semiconductor device; at least one conjugated organic buffer layer supported by the substrate and filtering a fluid; An apparatus comprising at least one ink-jet printed conjugated organic deposit provided on at least one conjugated organic buffer layer and forming a semiconductor-emitted display when a stimulus is applied. 10. The apparatus according to claim 9, wherein each conjugate organic deposit emits light when the fluid sample diffuses into the conjugate deposit and is stimulated. 11. The electrical conductivity of each conjugated organic deposit further comprising a pair of first and second electrodes provided in each conjugated organic deposit and sensing electrical conductivity in the conjugated organic deposit. 10. The apparatus of claim 9, wherein the variance changes when the fluid sample diffuses into the conjugated organic sediment and is stimulated. 12. A method of manufacturing a semiconductor device capable of emitting a display in response to a stimulus, comprising: supporting at least one first electrode on a substrate; Supporting at least one conjugated organic buffer layer on the electrodes such that the conjugated organic buffer layers are in contact with the respective first electrodes, inkjet printing at least one conjugated organic material on the at least one first electrode; Providing a respective conjugated organic deposit in contact with at least one conjugated organic buffer layer and supporting at least one second electrode on the topmost conjugated organic buffer layer. 13. Supporting at least one second electrode on the uppermost conjugated organic buffer layer comprises inkjet printing at least one organic mask in contact with the uppermost conjugated organic buffer layer; The at least one organic mask contacts the uppermost conjugated organic buffer layer with a weak adhesive force, and supports the second electrode material in contact with the uppermost conjugated organic buffer layer and the at least one organic mask. The two-electrode material contacts the uppermost conjugated organic buffer layer and at least one organic mask with a strong adhesive force, affixes an adhesive sheet to the second electrode material, removes the adhesive sheet, and removes at least one organic mask and at least one organic mask. The method according to claim 12, further comprising the steps of simultaneously removing the second electrode material on the organic mask. 14. The method according to claim 1, wherein at least one second conjugated organic buffer layer is formed on the conjugated organic buffer layer.
The step of supporting the electrodes includes a step of applying a shadow mask to a region of the uppermost conjugated organic buffer layer where the second electrode material is not deposited using the partition, and inkjet printing the second electrode material between the partitions. 13. The method of claim 12, wherein: 15. A method of manufacturing a semiconductor device capable of emitting a display in response to a stimulus, comprising: supporting a plurality of source electrodes on a substrate; and providing a plurality of gate electrodes on the substrate. Supporting a plurality of transistors between a plurality of source electrodes and a plurality of gate electrodes;
Here, each transistor has a source terminal connected to the source electrode, a gate terminal connected to the gate electrode, and a drain terminal. The second electrode is supported on the plurality of transistors, and the drain terminal of the plurality of transistors is provided. And supporting a conjugated organic buffer layer between the plurality of transistors and the second electrode in contact with the second electrode, and jet ink-printing a plurality of conjugated organic deposits on each transistor to form a plurality of conjugated organic deposits. A method comprising the steps of bringing the organic deposit into contact with the conjugated organic buffer layer and the second electrode. 16. A method of manufacturing a semiconductor device capable of emitting a corresponding display when a stimulus is applied, the method comprising: inkjet printing at least one conjugated organic deposit on a substrate; A method comprising supporting a first conjugated organic buffer layer on a conjugated organic deposit such that each conjugated organic deposit contacts the first conjugated organic buffer layer. 17. Supporting at least one pair of first and second electrodes on the substrate prior to the step of inkjet printing at least one conjugated organic deposit on the substrate, wherein each conjugated organic deposit comprises a pair of electrodes. 17. The method of claim 16, including the step of allowing the first and second electrodes to be ink-jet printed. 18. An ink jet printing method, further comprising at least one additional layer having at least one conjugated organic deposit over the first conjugated organic buffer layer, wherein each additional layer having at least one conjugated organic deposit is provided. Each further supporting a conjugated organic buffer layer over the layer, such that each additional layer having at least one conjugated organic deposit contacts the additional conjugated organic buffer layer 17. The method of claim 16, further comprising: 19. At least one pair of at least one additional layer having at least one conjugated organic deposit on the first conjugated organic buffer layer prior to inkjet printing the first conjugated organic buffer layer. 19. The method of claim 18, further comprising supporting the first and second electrodes so that respective conjugated organic deposits are inkjet printed on the pair of first and second electrodes. The described method. 20. A light emitting system for displaying an image, comprising: a substrate supporting the light emitting system; at least one first electrode supported by the substrate; and a current flowing between the substrate and the at least one first electrode. At least one second electrode for flowing current, at least one conjugated organic buffer layer supported between the at least one first electrode and the at least one second electrode, for controlling current flow, and At least one first electrode supported by the substrate, at least one second electrode supported by the substrate, wherein at least one first electrode
An electrode for flowing a current between the electrode and the at least one second electrode; at least one electrode supported between the at least one first electrode and the at least one second electrode for controlling the flow of the current; A plurality of conjugated organic buffer layers, a plurality of inkjet printed conjugated organic deposits each being in contact with at least one conjugated organic buffer layer and provided between one first electrode and one second electrode. A conjugated organic deposit that emits an indication when a voltage stimulus is applied to the first electrode and the second electrode; and a voltage stimulus selectively to the at least one first electrode and the at least one second electrode. Lighting system comprising a voltage source for applying a voltage. 21. The substrate and the at least one first electrode are transparent, and the plurality of conjugated organic deposits are comprised of a conductive material, and corresponding to at least one conjugated organic deposit when a voltage stimulus is applied. And stimulating the current to flow partially through each conjugated organic buffer layer in contact with the conjugated organic deposit, wherein at least one conjugated organic buffer layer comprises a luminescent material and emits light when the current flows. 21. The system of claim 20, wherein: 22. At least one group of continuous conjugated organic deposits is printed, wherein the group of continuous conjugated organic deposits forms a luminescent logo when current flows through at least one conjugated organic buffer layer. 22. The system of claim 21, wherein: 23. A plurality of groups of independent conjugated organic deposits are printed, the density of each group of conjugated organic deposits is substantially constant, and the plurality of printed groups comprises at least one conjugated organic buffer layer. 22. The system of claim 21, wherein a grayscale luminescent image is formed when a current flows through the system. 24. The substrate and at least one first electrode are transparent, the plurality of conjugated organic deposits are arranged in groups and arranged in a regular array, each group being capable of emitting red, green and blue light. 21. The system of claim 20, comprising three types of conjugated organic deposits made of guest material, wherein the ordered array constitutes a multicolor luminescent display when current flows through the conjugated organic deposits. 25. The substrate, wherein the substrate and at least one first electrode are transparent, the plurality of conjugated organic deposits comprise a luminescent guest material, and at least one conjugated organic buffer layer comprises a luminescent host material; Is partially diffused into the host material, multiple conjugated organic deposits are grouped and arranged in a regular array, and each group consists of three types of guest materials that can emit red, green, and blue light. Conjugated organic deposits, the band gap width and energy level of the guest material do not exceed that of the host material, so that each group emits red, green, and blue when a voltage stimulus is applied. 21. The method of claim 20, wherein the ordered array forms a multicolor light emitting display when current flows through the conjugated organic deposit. System. 26. A light emitting system for forming an image, comprising: a substrate for supporting the light emitting system; a plurality of source electrodes supported on the substrate for inducing a current flow; A plurality of gate electrodes for controlling flow, supported between the plurality of source electrodes and the plurality of gate electrodes, each comprising a source terminal connected to the source electrode, a gate terminal connected to the gate electrode, and a drain terminal, A plurality of transistors for controlling the flow of current, a second electrode supported by the plurality of transistors and facilitating the flow of current between the plurality of transistors and a drain terminal of the plurality of transistors; Drain terminal and second
A conjugated organic buffer layer supported to contact the electrodes and controlling the current flowing between the drain terminals of the plurality of transistors and the second electrode; supported on each of the transistors in contact with the conjugated organic buffer layer; A plurality of inkjet-printed conjugated organic deposits that emit an indication when a voltage stimulus is applied to the source electrode and the second electrode; and a plurality of source and second electrodes electrically connected to the light emitting system. A light emitting system including a voltage source for applying a voltage stimulus. 27. The substrate and at least one first electrode are transparent, the plurality of conjugated organic deposits are arranged in groups and arranged in a regular array, and each group is capable of emitting red, green, and blue light. 27. The system of claim 26, comprising three conjugated organic deposits of a material, wherein the ordered array forms a multicolor luminescent display when current flows through the conjugated organic deposit. 28. The substrate, wherein the substrate and the at least one first electrode are transparent, the plurality of conjugated organic deposits comprise a luminescent guest material, the at least one conjugated organic buffer layer comprises a luminescent host material, Is partially diffused into the host material, multiple conjugated organic deposits are grouped and arranged in a regular array, and each group consists of three types of guest materials that can emit red, green, and blue light. Conjugated organic deposits, the band gap width and energy level of the guest material do not exceed that of the host material, so that each group emits red, green, and blue when a voltage stimulus is applied. 27. The method of claim 26, wherein the ordered array forms a multicolor light emitting display when current flows through the conjugated organic deposit. System.