TWI640041B - Methods for high-resolution patterning of multiple layers side by side - Google Patents

Abstract

The present invention provides a method for fabricating a device comprising a first patterned device layer at a first location on a single substrate and a second patterned device layer at a second location. The method includes: depositing a first intermediate layer on the substrate; patterning the first intermediate layer, thereby removing the first intermediate layer at the first locations; depositing a first device layer; depositing a first a second intermediate layer; patterning the second intermediate layer and the underlying layer thereof, thereby removing the second intermediate layer and the underlying layers at the second locations; depositing a second device layer; and subsequently patterning The first device layer and the second device layer are formed to form the first patterned device layer at the first locations and the second patterned device layer at the second locations.

Description

High-resolution patterning method for side by side multilayer

The present invention relates to high resolution patterning for side-by-side multilayers and high resolution patterning for side-by-side multilayer stacking.

More particularly, the present invention relates to a high resolution method for forming non-overlapping patterns of different organic semiconductor layers and non-overlapping patterns for forming a layer stack including at least one organic semiconductor layer.

The method of the present invention can be advantageously used for high-resolution full-color light detection of high-resolution organic electronic devices (for example, high-definition full-color displays such as achromatic filters, and achromatic filters). And a manufacturing process of a photodetector array or a smart pixel or pixel array having a plurality of integrated organic photodetectors and organic light emitting diode sub-pixel elements.

For the manufacture of organic semiconductor based displays and imagers, a reliable and high resolution patterning method is required. Preferably, the patterning method also allows patterning of different organic semiconductor layers or different layer stacks side by side on a substrate, for example, to achieve multicolor emission in an OLED (Organic Light Emitting Diode) display or multicolor in an imager. Sensitivity.

Several patterning methods are suggested and implemented.

For example, one of the commonly used patterning techniques for organic electronic devices is based on shadow masking technology. By using a fine metal cover in a vacuum system The mask acts as a shadow mask to directly pattern the organic semiconductor during evaporation. This technology allows for defining features of one size of approximately 30 microns or greater. One of the disadvantages of this method is that it does not allow for very precise alignment. A further disadvantage of shadow masking technology is that it requires considerable cumbersome hardware maintenance and it cannot be scaled up to a large substrate size.

Additive techniques such as the extensive study of inkjet printing provide resolution similar to one of the shadow masks. However, additive techniques are not suitable for complex layer stacks such as multilayer stacking. For example, precise alignment can be difficult.

Several other patterning programs are emerging, such as, for example, self-assembly (eg, based on the use of a spin casting process on a pre-patterned substrate). This procedure requires careful selection of the repulsive/attractive patterned material for a particular organic layer of action. Another example of a revealing patterning method is laser induced forward transfer (LIFT). Using this procedure, the resolution is limited to 5 to 10 microns and the thermal transfer procedure used can degrade the electrical characteristics of the organic device.

The most promising technology for photolithography in a reproducible manner and achieving a pattern resolution of less than 10 microns on a large wafer size. However, the use of a photolithography procedure in combination with an organic semiconductor is not straightforward because most solvents used in standard photoresists and solvents used for photoresist development and/or photoresist stripping are soluble or damaged. Organic layer.

The lithographic patterning of the organic layer can be accomplished using orthogonal processing in which a fluorinated photoresist is used. This method provides micron resolution to standard photolithography equipment. For example, a method for fabricating a multi-color OLED device using orthogonal processing is described in US 2013/0236999, in which a plurality of luminescent layers or layer stacks (each emitting a different color of light) are deposited side by side and patterned in a single A plurality of light emitting elements are formed on the substrate. One of the disadvantages of this method is that the manufacture of fluorinated products is very expensive and the handling thereof is also very expensive and cumbersome.

A method of fabricating an organic electroluminescent display is described in US 2012/0252150, in which a different conventional organic electroluminescent element corresponding to a different color is formed by photolithography using a standard conventional photoresist. The method is based on the use of, for example, a water soluble material (p. a mask layer), a material that is insoluble in one of the photoresist liquid (the second mask layer) and one of the photoresist layers is stacked. In this way, the underlying organic compound layer can be patterned and the risk of dissolution or damage by one of the liquids used during photolithography patterning can be reduced. The first mask layer and the second mask layer can be left and used to protect the patterned organic compound layer in a further step, such as the step of forming other patterned organic compound layers.

The present invention is directed to a method for forming a non-overlapping pattern of a plurality of layers such as an organic semiconductor layer and forming a non-overlapping pattern of different layer stacks by side-by-side on a substrate by photolithography, wherein a conventional photoresist material can be used and the phase therein The risk of damage or degradation of the layer or layer stack caused by the lithography procedure is reduced compared to known methods.

The present invention provides a method for fabricating a device comprising a first patterned device layer at a first location on a single substrate and a second patterned device layer at a second location, the method comprising Depositing a first intermediate layer on the substrate; patterning the first intermediate layer, thereby removing the first intermediate layer at the first locations; depositing a first device layer; depositing a second intermediate layer Patterning the second intermediate layer and the underlying layers, thereby removing the second intermediate layer and the underlying layers at the second locations; depositing a second device layer; and subsequently patterning the The first device layer and the second device layer form the first patterned device layer at the first locations and the second patterned device layer at the second locations.

A method of the present invention may further include: before patterning the first device layer and the second device layer: depositing a third intermediate layer; patterning the third intermediate layer and the underlying layers, thereby Removing the third intermediate layer and the underlying layers at the location; and depositing a third device layer. These steps can be repeated to form additional patterned device layers at additional locations. The entire device layer is then patterned, i.e., the patterning of the device layers is completed in a single patterning process after all of the device layers have been deposited.

In an embodiment of the invention, the first device layer may be stacked on at least one of two layers and/or Alternatively, the second device layer can be stacked in at least one of the two layers and/or the third device layer can be stacked in at least one of the two layers and/or any additional device layer can be stacked in at least one of the two layers.

The first device layer, the second device layer, the third device layer, and any additional device layers can, for example, comprise an electroluminescent layer, a photosensitive layer, or a semiconductor layer. For example, the first device layer may include a first organic semiconductor layer, the second device layer may include a second organic semiconductor layer, and the third device layer may include a third organic semiconductor layer.

In an embodiment of the invention, the first intermediate layer, the second intermediate layer, the third intermediate layer, and any additional intermediate layers or further intermediate layers are a water soluble layer or an alcohol soluble layer. The intermediate layer may contain a polymer such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose, polyethylene glycol, polyglycerol or amylopectin, and the invention is not limited thereto. The intermediate layer may further comprise a solvent comprising water and/or an alcohol. The alcohol may, for example, be an alkoxy-free alcohol, for example, such as isopropyl alcohol, and the invention is not limited thereto. The alcohol can, for example, be a water soluble alcohol. The solvent may contain only water, only alcohol or a mixture of water and a water-soluble alcohol.

In an embodiment of the present invention, the step of patterning the first device layer, the second device layer, and the third device layer may include providing coverage of the first locations, the second locations, and the third One of the locations is patterned with a photoresist layer; an etching step is performed using the patterned photoresist layer as a mask; the etching is continued until the substrate is exposed; and the first intermediate layer and the second intermediate layer are And the third intermediate layer is dissolved in water or alcohol. The patterned photoresist layer can be removed prior to dissolving the first intermediate layer, the second intermediate layer, and the third intermediate layer. As an alternative to continuing the etching until the substrate is exposed, the etching may continue until the first intermediate layer is exposed or until at least a portion of the first device layer at a location other than the first locations is removed.

In an embodiment of the invention, the step of patterning the first device layer, the second device layer, and the third device layer may include: depositing a further intermediate layer; performing an etching step until the first intermediate layer is exposed And dissolving the first intermediate layer in water or alcohol. Make To continue the etching until an alternative to the first intermediate layer exposure, the etching may continue until at least a portion of the first device layer at a location other than the first locations is removed.

In an embodiment of the invention, the step of patterning the first device layer, the second device layer, and the third device layer may include: depositing a further intermediate layer; providing coverage of the first locations, the first Two locations and one of the third locations are patterned photoresist layers; performing an etching step using the patterned photoresist layer as a mask, continuing the etching until the substrate is exposed; and causing the first intermediate The layer, the second intermediate layer, the third intermediate layer, and the further intermediate layer are dissolved in water or alcohol. The patterned photoresist layer can be removed prior to dissolving the first intermediate layer, the second intermediate layer, the third intermediate layer, and the further intermediate layer. As an alternative to continuing the etching until the substrate is exposed, the etching may continue until the first intermediate layer is exposed or until at least a portion of the first device layer at a location other than the first locations is removed.

In an embodiment of the invention, the step of patterning the first device layer, the second device layer, and the third device layer may include: depositing a further intermediate layer; providing coverage of the first locations, the first Two locations and one of the third locations are patterned photoresist layers; performing a first etching step using the patterned photoresist layer as a mask, continuing the first etching step until the substrate is exposed; Except the patterned photoresist layer; performing a second etching step until the second intermediate layer is exposed; and dissolving the first intermediate layer and the second intermediate layer in water or alcohol. As an alternative to continuing the second etch until the second intermediate layer is exposed, the second etch may continue until the first intermediate layer is exposed or until the first device is removed at a location other than the first locations At least part of the layer.

One method of the present invention can advantageously be used to fabricate organic semiconductor-based devices and circuits having side-by-side different organic materials or patterns of different material stacks on a substrate (for example, such as a multi-color organic photodetector (OPD) Or a multi-color organic light-emitting diode (OLED) or one of an organic smart pixel (including an array of such devices) comprising at least one OLED sub-pixel element and at least one OPD sub-pixel element.

One method of the present invention can be used, for example, in a high-definition multi-color OLED display or a high-definition multi-color photodetector array manufacturing process for achromatic filters, which allows for obtaining a shadow mask than currently used. Higher resolution of technology. For example, one of the methods of the present invention can also be used to pattern micron-sized or sub-micron-sized pixel arrays of organic CMOS imagers.

In known procedures for photolithographic patterning of organic semiconductors, groups of sub-pixel elements (such as sub-pixel elements representing a single color in a multi-color display or imager) are successively patterned. Light lithography patterning of a sub-pixel element is performed directly after deposition of the corresponding electroluminescent layer stack. One of the disadvantages of this known method is that the sensitive organic semiconductor layer or layer stack is exposed multiple times to products (such as photoresists, developers, photoresist strippers) used during photolithography. While such products may be made to favor the underlying materials, multiple deposition and stripping of such products may pose a risk of degradation or damage to the underlying layers. Moreover, during partial removal of the electroluminescent layer stack, the sidewalls of the already patterned sub-pixel elements are exposed to an environment that can cause degradation or damage.

An advantage of an embodiment of the present invention is that during photolithographic patterning, each device layer can be always protected at a location where the device layer is part of the final device. Thus, methods in accordance with embodiments of the present invention can be advantageously used to pattern device layers (eg, such as organic device layers) that can be degraded by or negatively affected by products used during photolithography. In the method of the present invention, direct contact between such products and the layers of such devices can be avoided.

An advantage of an embodiment of the present invention is that conventional photolithographic products (photoresist, developer), i.e., photolithographic products that have been used in the microelectronics industry, can be used. An advantage of an embodiment of the present invention is that an expensive product such as a fluorinated photoresist is not required.

One advantage of one of the methods in accordance with an embodiment of the present invention is that it can be scaled up and is compatible with existing semiconductor process lines.

An advantage of one of the methods according to an embodiment of the invention is for patterning the packages The maximum processing temperature of the layer can be less than 150 °C. Therefore, the method can be applied to a flexible foil substrate (for example, such as on polyethylene naphthalate (PEN) foil or polyethylene terephthalate (PET) foil), thus achieving Manufacturing of flexible organic devices and circuits with high resolution.

One advantage of one of the methods according to embodiments of the present invention is that it can be cost effective and well controlled.

Certain objects and advantages of various aspects of the invention have been described above. Of course, it should be understood that not all such objects or advantages are necessarily achieved in accordance with any particular embodiment of the invention. Thus, for example, one skilled in the art will recognize that one of the advantages or advantages of the teachings may be achieved or optimized, and one of the other objects or advantages as may be. The invention is embodied or embodied. In addition, it should be understood that the summary is only an example and is not intended to limit the scope of the invention. The invention (as to both the organization and the method of operation), as well as its features and advantages, may be best understood by reference to the following detailed description.

1‧‧‧ first opening

2‧‧‧second opening

3‧‧‧ third opening

10‧‧‧Substrate

11‧‧‧First bottom electrode

12‧‧‧second bottom electrode

13‧‧‧ Third bottom electrode

21‧‧‧First intermediate layer

22‧‧‧Second intermediate layer

23‧‧‧ Third intermediate layer

24‧‧‧ Further intermediate layer

31‧‧‧First device layer/first device layer stacking

32‧‧‧Second device layer

33‧‧‧ third device layer / third layer stack

40‧‧‧ photoresist layer

311‧‧‧First patterned device layer/first sub-pixel

321‧‧‧Second patterned device layer/second sub-pixel

331‧‧‧ Third patterned device layer/third sub-pixel

d _ov ‧ ‧ overlapping

1(a) through 1(i) illustrate a sequence of program steps in accordance with one of the methods of the present invention.

2(a) through 2(d) illustrate the procedural steps of a method for removing excess material based on photolithography using a benign photoresist system in accordance with the present invention.

3 illustrates a patterned photoresist layer extending beyond one of the edges of an opening made in an intermediate layer. Figure 3 (a) shows a cross section; Figure 3 (b) shows a top view.

4(a) through 4(c) illustrate the procedural steps of a method for removing excess material based on the use of a further intermediate layer in accordance with the present invention.

5(a) through 5(c) illustrate the procedural steps of a method for removing excess material using a further intermediate layer based on combined photoresist patterning and a single etching step in accordance with the present invention.

6(a) to 6(d) illustrate patterning based on combined photoresist and two according to the present invention The etching step uses a further intermediate layer of procedural steps for removing one of the excess materials.

Any reference signs in the claims should not be construed as limiting the scope of the invention.

In the different figures, the same reference symbols are used to refer to the same or similar elements.

In the following detailed description, numerous specific details are set forth However, it is to be understood that the invention may be practiced without the specific details. In other instances, well-known methods, procedures, and techniques are not described in detail to avoid obscuring the invention.

The invention will be described with respect to particular embodiments and with reference to certain drawings, but the invention is not limited thereto but only by the scope of the claims. The drawings described are only illustrative and not limiting. In the drawings, the size of some elements may be exaggerated and not drawn to scale for illustrative purposes. The dimensions and relative dimensions do not necessarily correspond to actual reductions in the practice of the invention.

In addition, the terms first, second, third and similar in the description and the scope of the claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. The terms are interchangeable under appropriate circumstances and can operate differently than the sequences described or illustrated herein.

In addition, the terms top, bottom, over, under, and the like in the description and the claims are used for descriptive purposes and are not necessarily used to describe relative positions. It is understood that the terms so used are interchangeable under the appropriate circumstances and the embodiments of the invention described herein are capable of operation in an orientation other than those described or illustrated herein.

The term "comprising", used in the claims, is not to be construed as limited It is to be understood that the existence of the recited features, integers, steps or components are recited, but does not exclude the presence or addition of one or more features, integers, steps or components or the like. Therefore, the expression "a device includes components The scope of A and B" should not be limited to devices consisting only of components A and B.

The method of the present invention can be advantageously used for high resolution patterning of layers or layer stacks of materials that affect the degradation stage of products (such as photoresists, developers, and strippers) used during conventional photolithography. Such materials include, for example, organic semiconductors, organic dielectrics, quantum dots, ionic conductors, organic structures, reactive metals or salts.

In further description, a method of the invention in which, for example, a device layer or a device layer stack comprises an organic semiconductor material is described. In the further description and in the scope of the claims, "device layer" may refer to a single layer and a stack of at least two layers.

The program steps of an example of one of the methods according to the present invention are schematically illustrated in Figures 1(a) through 1(i). As an example, the program steps for the manufacture of a three color OLED are shown. The figures show a cross section corresponding to a single OLED comprising one of the three sub-pixels.

The program can also be used to fabricate a plurality of three color OLEDs (corresponding to a plurality of pixels) on a single substrate, such as, for example, an array of three color OLEDs configured in a plurality of columns and a plurality of rows. More generally, the program can be used to form side-by-side patterned layer stacks having different properties (eg, different colors in an OLED or in an OPD or multiple functions in a circuit) and fabricating such patterned layers Stacked arrays.

In the context of the present invention, a pixel refers to a single image point in an imager or a display. In an imager or a display, a plurality of pixels are typically arranged in columns and rows. Each pixel may be composed of sub-pixels, each of which corresponds to a different color, for example. Each sub-pixel includes a pixel element, such as a light-emitting element (such as an OLED) or a light-detecting element (such as an organic photodetector).

1(a) schematically shows a substrate 10 having a first bottom electrode 11, a second bottom electrode 12 and a third bottom electrode 13 on a surface. In the final device, the first bottom electrode 11 is a bottom electrode of one of the first sub-pixels (first color), and the second bottom electrode 12 is a bottom electrode of the second sub-pixel (second color) and the third bottom The electrode 13 is a bottom electrode of one of the third sub-pixels (third color). There may be an edge at the edge of the bottom electrode A cover layer (not shown) provides protection from short circuits and leakage. This edge covering layer can be made of an organic or inorganic material having good electrical insulating properties. Substrate 10 can be a glass substrate or a flexible foil substrate or any other suitable substrate known to those skilled in the art. The bottom electrode may, for example, comprise ITO (Indium Tin Oxide), Mo, Ag, Au, Cu, such as, for example, PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) A conductive polymer or a conductive CNT (carbon nanotube) or graphene layer, but the invention is not limited thereto.

A first intermediate layer 21 is provided on the substrate 10 as shown in Figure 1 (a). The first intermediate layer 21 does not result in a further degradation of one of the device layers or device layer stacks in the program. The first intermediate layer can be, for example, a water based material or an alcohol based material. The first intermediate layer may contain a polymer such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, water soluble cellulose, polyethylene glycol, polyglycerol or amylopectin. The first intermediate layer may further contain a solvent including water and/or an alcohol. The alcohol may, for example, be an alkoxy-free alcohol, such as, for example, isopropanol. The alcohol can be, for example, a water soluble alcohol. The solvent may contain only water, only alcohol or a mixture of water and a water-soluble alcohol. The thickness of the first intermediate layer 21 may be, for example, in the range of between 100 nm and 6000 nm (for example, between 500 nm and 2000 nm), but the invention is not limited thereto.

As illustrated in FIG. 1(b), the first intermediate layer 21 is then patterned, thereby forming a first opening 1 through the first intermediate layer 21 and exposing the first bottom electrode 11. The first intermediate layer 21 can be patterned by conventional photolithography followed by dry etching (for example, using O ₂ , SF ₆ or CF ₆ plasma) or wet etching. Preferably, a solvent developable photoresist is used to pattern the first intermediate layer 21. However, the invention is not limited thereto and other photoresists may be used. The first opening 1 may have any suitable shape, such as, for example, a rectangular shape or a circular shape, although the invention is not limited thereto. The first bottom electrode 11 may be completely exposed or it may be exposed almost completely, which means that only the edge of the first bottom electrode 11 is still covered by the first intermediate layer 21. After this step, the second bottom electrode 12 and the third bottom electrode 13 are still covered by the first intermediate layer 21.

In the next step, a first device layer 31 is deposited as depicted in Figure 1 (c). In this way, the first device layer 31 is in contact with the first bottom electrode 11. An example described here The first device layer 31 corresponds to a first color (first sub-pixel) and includes an organic semiconductor material suitable for emitting light of a first color (or first color).

In the example described herein (three-color OLED), the first device layer 31 may be, for example, a stack comprising, for example, a hole injection layer, an electron blocking layer, a hole transport layer, and an electroluminescence. The organic layer, an electron transport layer, a hole blocking layer, and/or an electron injecting layer are not limited thereto. The first device layer 31 includes at least one first electroluminescent organic layer. The first device layer can be deposited by solution processing (eg, spin coating, printing, spraying, slot coating, knife coating), vapor deposition (eg, CVD or OVPD), or vacuum deposition (eg, evaporation). 31.

After deposition of the first device layer 31, a second intermediate layer 22 is deposited on the first device layer 31, for example by spin coating, slit coating, dip coating, printing or knife coating (Fig. 1 (Fig. 1 d)), but the invention is not limited thereto. The second intermediate layer 22 does not result in a degradation of one of the device layers or stacks of device layers in the first device layer 31 and the program. It protects the first device layer or device layer stack from the effects of further products used in the photolithography step in the program. It may have the same composition as the first intermediate layer 21 or it may have a different composition.

Next, as illustrated in FIG. 1(e), the second intermediate layer 22 and the underlying layer (the first device layer 31 and the first intermediate layer 21) are patterned, whereby only at the position of the second bottom electrode 12 A second opening 2 is formed through one of the layers and the second bottom electrode 12 is exposed. Patterning of the second intermediate layer 22 and the underlying layer can be accomplished by using a photolithography of a conventional photoresist. It is preferred to use a solvent developable photoresist. However, the invention is not limited thereto and other photoresists may be used. After the photolithography, an etching step is performed to partially remove the second intermediate layer 22, the first device layer 31, and the first intermediate layer 21. The etching step can be a wet etching step or a dry etching step (eg, using O ₂ , SFS, or CFS plasma), and a single etchant can be used to remove the different layers.

In the next step, a second device layer 32 is deposited as depicted in Figure 1 (f). With this The second device layer 32 is in contact with the second bottom electrode 12. In the examples described herein, the second device layer or device layer stack 32 corresponds to a second color and includes one of the organic semiconductor materials suitable for emitting light of a second color (or second color). The second device layer 32 can, for example, include a hole injection layer, an electron blocking layer, a hole transport layer, an electroluminescent organic layer, an electron transport layer, a hole blocking layer, and/or an electron injection. Layer, however, the invention is not limited thereto. The second device layer 32 includes at least one second electroluminescent organic layer. The second device layer can be deposited by solution processing (eg, spin coating, printing, spraying, slot coating, knife coating), vapor deposition (eg, CVD or OVPD), or vacuum deposition (eg, evaporation). .

The steps illustrated in Figures 1(d) through 1(f) are then repeated to form a third sub-pixel. After deposition of the second device layer 32, a third intermediate layer 23 is deposited on the second device layer 32 (Fig. 1(g)). The third intermediate layer 23 does not result in a layer of degradation of one of the device layers or device layer stacks to be further provided in the underlying device layer and the program. It protects the second device layer or device layer stack 32 from the effects of further use in the program for products in the photolithography step. The third intermediate layer may contain a polymer such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, water soluble cellulose, polyethylene glycol, polyglycerol or amylopectin. The third intermediate layer may further comprise a solvent selected from one of water and/or alcohol. The alcohol may, for example, be an alkoxy-free alcohol, such as, for example, isopropanol. The alcohol can be, for example, a water soluble alcohol. The solvent may contain only water, only alcohol or a mixture of water and a water-soluble alcohol.

Next, as illustrated in FIG. 1(h), the third intermediate layer 23 and the underlying layer (the second device layer 32, the second intermediate layer 22, the first device layer 31, and the first intermediate layer 21) are patterned, Thereby, a third opening 3 passing through one of the layers is formed and exposed at the position of the third bottom electrode 13 and the third bottom electrode 13 is exposed. Patterning of the third intermediate layer 23 and the underlying layer can be accomplished by using a photolithography of a conventional photoresist. It is preferred to use a solvent developable photoresist. However, the invention is not limited thereto and other photoresists may be used. After the photolithography, an etching step is performed to partially remove the third intermediate layer 23, the second device layer 32, the second intermediate layer 22, the first device layer 31, and the first intermediate layer 21. The etching step can be a wet etching step or a dry etching step (eg, using O ₂ , SFS, or CFS plasma), and a single etchant can be used to remove the different layers.

In the next step, a third device layer 33 is deposited as depicted in Figure 1(i). In this way, the third device layer 33 is in contact with the third bottom electrode 13. In the example described herein, the third device layer 33 corresponds to a third color and includes one of the organic semiconductor materials suitable for emitting light of a third color (or third color). The third layer stack 33 can, for example, include a hole injection layer, an electron blocking layer, a hole transport layer, an electroluminescent organic layer, an electron transport layer, a hole blocking layer, and/or an electron injection. Layer, however, the invention is not limited thereto. The third device layer 33 includes at least one third electroluminescent organic layer. The third device layer can be deposited by solution processing (eg, spin coating, printing, spraying, slot coating, knife coating), vapor deposition (eg, CVD or OVPD), or vacuum deposition (eg, evaporation). .

After depositing a desired number of device layers or colors (three in the example depicted in Figures 1(a) through 1(i)), the different layers are removed at locations that do not require different layers in the final device. , that is, the different layers are patterned. This removal can be accomplished in different ways, as further illustrated: (i) photolithography using a benign photoresist system; (ii) using a further intermediate layer; (iii) bonding photoresist patterning and a single etch The step uses a further intermediate layer; and (iv) a photoresist intermediate patterning and two etching steps using a further intermediate layer.

The first method for removing excess material is based on the use of a benign photoresist system (ie, a photoresist system that does not cause degradation of the exposed layer (ie, the layer in direct contact with the photolithographic product)) Light lithography. A conventional photoresist system can be used in the case where the exposed layer is not degraded or damaged by the product used during photolithography. A fluorinated photoresist system can be used where the exposed layer is degraded or damaged by conventional photoresist products. The program steps of this method are schematically illustrated in Figures 2(a) to 2(d).

In this method, a photoresist layer is deposited on the structure of FIG. 1(i) which does not cause degradation of the exposed layer of the multilayer stack (third device layer 33 in this example). As illustrated in FIG. 2(a), the photoresist layer 40 is patterned such that it remains in the first opening 1 (first position) corresponding to the first intermediate layer 21, and the second intermediate layer 22 The position of the second opening 2 (second position) and the third opening 3 (third position) of the third intermediate layer 23. Therefore, this patterning step is completed for all sub-pixels (all colors, all device layers) at the same time. The patterned photoresist layer 40 can match the previously made openings (1, 2, 3) in the intermediate layer (21, 22, 23), or it can extend beyond the edges of such openings. In the example shown in Figure 2(a), the photoresist layer 40 extends beyond the edges of the openings (i.e., overlaps with them). For an example of an open-centered square, between the photoresist layer 40 and one of the openings in FIG. 3(a) (cross-section) and FIG. 3(b) (top view) Overlap d _ov . For reasons of clarity, the device layers and electrode layers are not shown in this figure.

After patterning the photoresist layer 40 (eg, by illumination and development through a shadow mask), the exposed regions (ie, regions not covered by the patterned photoresist layer 40) are removed by etching. In the middle and lower layers. For example, RIE etching (eg, oxygen, NO ₂ , SF ₆ , CF ₄ ) can be used to remove undesirable or unwanted materials. In embodiments of the invention, the etch may, for example, continue (eg, using the same etchant) until the substrate 10 is exposed. This etching step can be a time controlled etch. A cross section of the resulting structure is shown in Figure 2(b).

In an alternate embodiment (not shown), the etching may continue until the first intermediate layer 21 is exposed. In these embodiments, the first intermediate layer 21 is preferably thicker than the first device layer 31 and the second device layer 32. Under such conditions, after the etching step, at least a portion of the second intermediate layer 22 still covers the first device layer 31 at the first location and at least a portion of the third intermediate layer 23 still covers the second device at the second location Layer 32. The third device layer 33 is covered by the photoresist layer 40 during etching. The advantage is that all device layers are protected at least at the location where the sub-pixels are to be formed during the etching step.

In another alternative embodiment (not shown), the etching may continue until the first electroluminescent layer (the portion of the first device layer stack 31) is removed at a location other than the first location. In this way, the electroluminescent layers of different sub-pixels (different colors) are separated from one another.

After the etching step, the photoresist layer 40 can be removed (as shown in Figure 2(c)). Then borrow All of the excess layer was removed by coating one of the intermediate layers 21, 22 and 23 to dissolve one of the solutions. This dissolving solution can be, for example, water or an alcohol depending on the particular material (water soluble or alcohol soluble) used in the intermediate layer.

In an alternative procedure (not shown), the step of removing the photoresist layer 40 by coating one of the intermediate layers 21, 22 and 23 to dissolve the photoresist layer 40 and the step of removing the excess layer without a photoresist The layer 40 was previously removed.

After processing the sample with the dissolution solution, a structure as shown in FIG. 2(d) is obtained, the structure including one of the first patterned device layers 311 at the first position side by side, and one of the second positions The patterned device layer 321 and one of the third patterned device layers 331 at the third location.

One of the advantages of the method illustrated in FIG. 2 is to protect the first device layer 31 and the second device layer 32 at least at locations where the first sub-pixel 311 and the second sub-pixel 321 are formed during the entire process. These device layers are only exposed at these locations to the dissolution solution used to remove the intermediate layer. In the example shown, the third device layer 33 is exposed to the photoresist 40 and the product used during photolithography. Therefore, this method is suitable for applications in which the third device layer 33 does not damage or degrade one of the robust layers without such lithographic products. Fluorescent photoresist systems can be used where the third device layer 33 is not sufficiently resistant to the effects of conventional lithographic products.

A second method for removing excess material is based on the use of a further intermediate layer. The program steps of this method are schematically illustrated in Figures 4(a) to 4(c). One advantage of this second method is that all device layers 31, 32, 33 are protected at least at locations where the first sub-pixel 311, the second sub-pixel 321 and the third sub-pixel 331 are formed during the entire program. The device layer is exposed only to the dissolved solution used to remove the intermediate layer at these locations.

In this second method, a further intermediate layer 24 is deposited on the structure of Figure 1 (i). The further intermediate layer 24 can be a planarization layer as illustrated in Figure 4(a) or it can be a non-planarized layer (conformal or semi-conformal). Further intermediate layer 24 may contain a polymer such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, water soluble cellulose, polyethylene glycol, polyglycerol or Amylopectin. Further intermediate layers may further comprise a solvent selected to include water and/or alcohol. The alcohol may, for example, be an alkoxy-free alcohol, such as, for example, isopropanol. The alcohol can be, for example, a water soluble alcohol. The solvent may contain only water, only alcohol or a mixture of water and a water-soluble alcohol.

After depositing the further intermediate layer 24, a time controlled dry etching step or a wet etching step is completed. In an embodiment of the invention, the etching may continue until the first intermediate layer 21 is exposed (as depicted in Figure 4(b)). The first intermediate layer 21 is preferably thicker than the first device layer 31, the second device layer 32, and the third device layer 33. Under such conditions, after the etching step, at least a portion of the second intermediate layer 22 still covers the first device layer 31, at least a portion of the third intermediate layer 23 still covering the second device layer 32 and further at least a portion of the intermediate layer 24. The third device layer 33 is still covered at the position where the sub-pixels are to be formed. The advantage is that all device layers are protected at least at the location where the sub-pixels are to be formed during the etching step.

In an alternate embodiment (not shown), the etching may continue until at least the first electroluminescent layer (portion of the first device layer 31) is removed at a location other than the first location. In this way, the electroluminescent layers of different sub-pixels (different colors) are separated from one another.

Next, the first intermediate layer 21, the second intermediate layer 22, the third intermediate layer 23, and the further intermediate layer 24 are used to dissolve one of the solutions (water or alcohol) to remove the unnecessary layer, thereby resulting in FIG. 4(c). The structure shown includes one of the first patterned device layer 311 at a first position side by side, one of the second patterned device layer 321 at a second location, and a third warp pattern at a third location Device layer 331. One advantage of this method is that the first device layer 31, the second device layer 32, and the third device layer 33 at the locations where the sub-pixels are formed are protected by overlying the intermediate layer during the etching step. Therefore, this etching step does not damage the device layer.

A third method for removing excess material is based on a combined photoresist patterning and a single etching step using a further intermediate layer. One advantage of this method is that all device layers 31, 32, 33 are protected at least at locations where the first sub-pixel 311, the second sub-pixel 321 and the third sub-pixel 331 are formed during the entire program. The device layers are only exposed to these locations A solution for removing the intermediate layer and not exposed to the product used during photolithography. The program steps of this method are schematically illustrated in Figures 5(a) to 5(c).

In this method, a further intermediate layer 24 is deposited on the structure of Figure 1 (i). The intermediate layer 24 can be a planarization layer as shown in FIG. 5(a) or it can be a non-planarization layer (conformal or semi-conformal). Further intermediate layer 24 may contain a polymer such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, water soluble cellulose, polyethylene glycol, polyglycerol or amylopectin. The further intermediate layer may further comprise a solvent selected to include water and/or alcohol. The alcohol may, for example, be an alkoxy-free alcohol, such as, for example, isopropanol. The alcohol can be, for example, a water soluble alcohol. The solvent may contain only water, only alcohol or a mixture of water and a water-soluble alcohol.

After deposition of the further intermediate layer 24, a photoresist layer 40 is deposited and patterned, as depicted in Figure 5(a). It is preferred to use a solvent developable photoresist. However, the invention is not limited thereto and other photoresists may be used. The photoresist layer 40 is patterned such that it remains in the first opening 1 (first position) corresponding to the first intermediate layer 21, the second opening 2 (second position) in the second intermediate layer 22, and the third The position of the third opening 3 (third position) in the intermediate layer 23. Therefore, this patterning step is completed for all sub-pixels (all colors, all device layers) at the same time. The patterned photoresist layer 40 can match the previously made openings (1, 2, 3) in the intermediate layer (21, 22, 23), or it can extend beyond the edges of such openings. In the example shown in Figure 5(a), the photoresist layer 40 extends beyond the edge of the opening. For an example in which the opening is square, between FIG. 3(a) (cross section) and FIG. 3(b) (top view) schematically illustrate the relationship between the photoresist layer 40 and one of the openings in an intermediate layer. Overlap d _ov . For reasons of clarity, the device layers and electrode layers are not shown in this figure.

After patterning the photoresist layer 40 (eg, by illumination and development through a shadow mask), the exposed regions are removed by wet etching or dry etching (ie, not patterned by the photoresist layer) The layer in the 40 covered area until the substrate 10 is exposed. This is shown schematically in Figure 5(b). For example, RIE etching (eg, oxygen, NO ₂ , SF ₆ , CF ₄ ) can be used to remove undesirable materials.

In an alternate embodiment, the etching may continue until the first intermediate layer 21 is exposed. In another In an alternate embodiment (not shown), the etching may continue until at least the first electroluminescent layer (the portion of the first device layer stack 31) is removed at a location other than the first location. In this way, the electroluminescent layers of different sub-pixels (different colors) are separated from one another.

Next, the photoresist layer 40 can be removed and all of the excess layer removed by dissolving one of the intermediate layers 21, 22, 23, and 24 by coating. This solution can be, for example, water or an alcohol depending on the particular material used for the intermediate layer. After processing the sample with the dissolution solution, a structure as shown in FIG. 5(c) is obtained, the structure including one of the first patterned device layers 311 at the first position side by side on the substrate, at the second position a second patterned device layer 321 and a third patterned device layer 331 at a third location.

A fourth method for removing excess material is based on a combined photoresist patterning, a first etching step, and a second etching step using a further intermediate layer. The program steps of this method are schematically illustrated in Figures 6(a) to 6(d).

In this method, a further intermediate layer 24 is deposited on the structure of Figure 1 (i). The further intermediate layer 24 can be a planarization layer as shown in Figure 6(a) or it can be a non-planarization layer (conformal or semi-conformal).

After deposition of the further intermediate layer 24, a photoresist layer 40 is deposited and patterned, as depicted in Figure 6(a). It is preferred to use a solvent developable photoresist. However, the invention is not limited thereto and other photoresists may be used. The photoresist layer 40 is patterned such that it remains in the first opening 1 (first position) corresponding to the first intermediate layer 21, the second opening 2 (second position) in the second intermediate layer 22, and the third The position of the third opening 3 (third position) in the intermediate layer 23. Therefore, this patterning step is completed for all sub-pixels (all colors, all device layers) at the same time. The patterned photoresist layer 40 can match the previously made openings (1, 2, 3) in the intermediate layer (21, 22, 23), or it can extend beyond the edges of such openings. In the example shown in Figure 6(a), the photoresist layer 40 extends beyond the edge of the opening. For an example in which the opening is square, between FIG. 3(a) (cross section) and FIG. 3(b) (top view) schematically illustrate the relationship between the photoresist layer 40 and one of the openings in an intermediate layer. Overlap d _ov . For reasons of clarity, the device layers and electrode layers are not shown in this figure.

After patterning the photoresist layer 40 (eg, by illumination and development through a shadow mask), the exposed regions are removed by performing a first etching step (ie, not patterned by the photoresist layer) The area covered by 40 is under the volatilization layer until the substrate is exposed (Fig. 6(b)). For example, an RIE etch (eg, oxygen, NO ₂ , SF ₆ , CF ₄ ) can be used for the first etch step. Next, a second etching step is completed until the second intermediate layer 22 is exposed. In some embodiments, the second etching step can be continuous for one of the first etching steps. A cross section of the resulting structure is schematically shown in Figure 6(c).

In an alternative embodiment (not shown), the second etching step may continue until the first intermediate layer 21 is exposed. In other alternative embodiments (not shown), the second etching step may continue until at least the first electroluminescent layer (portion of the first device layer 31) is removed at a location other than the first location. In this way, the electroluminescent layers of different sub-pixels (different colors) are separated from one another.

After the second etching step, all of the remaining excess layer is removed by coating one of the intermediate layers 21 and 22 and further intermediate layer 24 to dissolve one of the solutions. This solution can be, for example, water or an alcohol depending on the particular material used for the intermediate layer. After processing the sample with the dissolution solution, a structure as shown in FIG. 6(d) is obtained, which includes one of the first patterned device layers 311 at the first position side by side, and one of the second positions The patterned device layer 321 and one of the third patterned device layers 331 at the third location.

In an embodiment of the invention, the device layer stack may comprise a complete OLED stack or the like may comprise an incomplete OLED stack. As an example of an incomplete stack, a stack can be deposited for each component/color up to the electroluminescent layer. After the patterning process described above, the remaining layer and a top electrode can then be deposited as a common stack.

The method of the present invention can be used to fabricate a device that includes a plurality of pixels, such as, for example, a two-dimensional array of pixels. For example, the methods of the present invention can be used to fabricate OLED arrays or OLED displays, such as multi-color displays (eg, RGB, RGBW) or displays that combine hyperspectral display with one or more colors. For example, the method of the invention can be used in manufacturing An OPD array or an OPD display, such as a multi-color display (eg, RGB, RGBW) or an imager that combines a hyperspectral display with one or more colors. The method of the present invention can also be used to fabricate OTFT or OTFT circuits with different semiconductors side by side or for fabricating biosensors. The method of the present invention can be used to fabricate "smart" pixels in which, for example, OPDs, OLEDs, and OTFTs (eg, RGB OLED + white OPD, OPD + read OTFT, OLED + read OTFT) are combined.

The foregoing description details certain embodiments of the invention. However, it should be understood that the present invention may be practiced in many ways, regardless of how the foregoing is presented in detail herein. It should be noted that when describing certain features or aspects of the invention, the use of a particular terminology should not be considered as implying that the terminology is re-defined herein to be limited to the inclusion of the features or aspects of the invention in connection with the terminology. Any specific feature.

While the above detailed description has been shown and described, the embodiments of the present invention Various omissions, substitutions, and changes are made in the details.

Claims (15)

A device for manufacturing one of a first patterned device layer (311) at a first location on a substrate (10) and a second patterned device layer (321) at a second location Method, the method comprising: depositing a first intermediate layer (21) on the substrate (10); patterning the first intermediate layer (21), thereby removing the first intermediate layer at the first locations Depositing a first device layer (31); depositing a second intermediate layer (22); patterning the second intermediate layer (22) and its underlying layer, thereby removing the second portion a second intermediate layer and the underlying layers; depositing a second device layer (32); and subsequently patterning the first device layer (31) and the second device layer (32) to form at the first locations The first patterned device layer (311) and the second patterned device layer (321) are formed at the second locations. The method of claim 1, further comprising: before patterning the first device layer (31) and the second device layer (32): depositing a third intermediate layer (23); patterning the third intermediate layer (23) and the underlying layers, thereby removing the third intermediate layer and the underlying layers at a third location; and depositing a third device layer (33), wherein the sequence of steps is repeated until a predetermined order is obtained A number of device layers. The method of claim 2, wherein patterning of all of the device layers is performed in a single patterning process after all of the device layers have been deposited. The method of any of the preceding claims, wherein the first intermediate layer (21), the second intermediate layer (22) and the third intermediate layer (23) are soluble in water or alcohol. The method of any one of claims 1 to 3, wherein the first device layer (31) is at least two One of the layers is stacked. The method of any one of claims 1 to 3, wherein the second device layer (32) is stacked in at least one of two layers. The method of any one of claims 1 to 3, wherein each of the device layers is stacked in at least one of two layers. The method of any one of claims 1 to 3, wherein the device layer comprises an electroluminescent layer, a photosensitive layer or a semiconductor layer. The method of any one of claims 1 to 3, wherein each of the device layers comprises a different organic semiconductor layer. The method of any one of claims 1 to 3, wherein the step of patterning the first device layer (31) and the second device layer (32) comprises: providing coverage of the first locations and the second One of the locations is patterned with a photoresist layer (40); an etch step is performed using the patterned photoresist layer (40) as a mask, the etching is continued until the substrate (10) is exposed; the Patterning the photoresist layer (40); and dissolving the first intermediate layer (21) and the second intermediate layer (22) in water or an alcohol. The method of any one of claims 1 to 3, wherein the step of patterning the first device layer (31) and the second device layer (32) comprises: depositing a further intermediate layer (24); performing an etch Steps until the first intermediate layer (21) is exposed; and the first intermediate layer (21) and the second intermediate layer (22) are dissolved in water or an alcohol. The method of any one of claims 1 to 3, wherein the step of patterning the first device layer (31) and the second device layer (32) comprises: Depositing a further intermediate layer (24); providing a patterned photoresist layer (40) covering the first locations and the second locations; using the patterned photoresist layer (40) as a mask And performing an etching step, continuing the etching until the substrate (10) is exposed; removing the patterned photoresist layer (40); and making the first intermediate layer (21) and the second intermediate layer (22) And the further intermediate layer (24) is dissolved in water or an alcohol. The method of any one of claims 1 to 3, wherein the step of patterning the first device layer (31) and the second device layer (32) comprises: depositing a further intermediate layer (24); providing coverage Waiting for the first location and one of the second locations to be patterned with a photoresist layer (40); using the patterned photoresist layer (40) as a mask to perform a first etching step, continuing the etching until The substrate (10) is exposed; the patterned photoresist layer (40) is removed; a second etching step is performed until the second intermediate layer (22) is exposed; and the first intermediate layer (21) is The second intermediate layer (22) and the further intermediate layer (24) are dissolved in water or an alcohol. A method for fabricating a multicolor organic light emitting diode array using the method of any one of claims 2-3, wherein the first patterned device layer (311) comprises a first chromatogram for emission a first electroluminescent layer, the second patterned device layer (321) comprising a second electroluminescent layer for emitting a second chromatogram, and the third device layer (33) comprises for emitting A third electrochromic layer of one of the third chromatograms. A method for fabricating a multicolor organic photodetector array using the method of any one of claims 2-3, wherein the first patterned device layer (311) comprises a first semiconductor layer of a first absorption spectrum, the second patterned device layer (321) includes a second semiconductor layer having a second absorption spectrum, and the third device layer (33) includes a first A third semiconductor layer of one of the three absorption spectra.