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WO2015014489A1 - Procédé de structuration d'une couche électriquement conductrice ou semi-conductrice - Google Patents

Procédé de structuration d'une couche électriquement conductrice ou semi-conductrice Download PDF

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Publication number
WO2015014489A1
WO2015014489A1 PCT/EP2014/002091 EP2014002091W WO2015014489A1 WO 2015014489 A1 WO2015014489 A1 WO 2015014489A1 EP 2014002091 W EP2014002091 W EP 2014002091W WO 2015014489 A1 WO2015014489 A1 WO 2015014489A1
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WO
WIPO (PCT)
Prior art keywords
layer
irradiation
conductivity
laser
regions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2014/002091
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German (de)
English (en)
Inventor
Moritz SCHAEFER
Malte Schulz-Ruhtenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of WO2015014489A1 publication Critical patent/WO2015014489A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H10P34/42—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/01—Manufacture or treatment
    • H10D86/021—Manufacture or treatment of multiple TFTs
    • H10D86/0221—Manufacture or treatment of multiple TFTs comprising manufacture, treatment or patterning of TFT semiconductor bodies
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/211—Changing the shape of the active layer in the devices, e.g. patterning by selective transformation of an existing layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition

Definitions

  • the present invention relates to a method for structuring an electrically conductive or semiconducting layer, by which one or more
  • Layer regions of the layer are electrically insulated, or by the electrical conductivity of one or more layer regions is set specifically.
  • Thin-film electronics in particular organic electronics, are based on thin layers of electrically conductive, semiconductive or insulating materials. Typical layer thicknesses are between a few 10 nanometers and a few micrometers. Particularly in the case of organic light-emitting diodes, thin-film transistors for LCDs or in thin-film photovoltaics, transparent electrodes are required in order to disconnect or couple in light. For this purpose, mostly transparent,
  • TCO electrically conductive oxides
  • Transparency is very often used indium tin oxide (ITO) as electrode material. Also transparent organic, electrically conductive materials are used. Examples of these are PEDOT: PSS (poly-3,4-ethylenedioxythiophene: polystyrene sulfonate) or
  • the transparent electrodes must be structured according to their application and electrically from each other be isolated.
  • Semiconducting layers must also be isolated between the individual components in order to avoid the so-called cross-talk between the components. In all cases, a structuring of an electrically conductive or semiconductive layer is thus required, by means of which a plurality of layer regions of the layer are electrically isolated from one another.
  • the structuring of transparent electrodes currently takes place, as a rule, by local removal of the electrically conductive layer.
  • the TCO material is locally removed by etching.
  • the TCO layer must be prepared by means of photoresist and lithography, for example by suitable masking.
  • Another possibility is to convert an amorphous TCO layer in certain areas selectively into a polycrystalline layer having the required electrical conductivity.
  • the remaining amorphous layer can then be removed with an etching process. After the etching process must be performed.
  • US 2010/0105196 A1 shows a method for structuring an ITO layer, in which initially an amorphous ITO layer is applied and subsequently converted into polycrystalline ITO by irradiation by means of a laser beam in the desired regions. The remaining amorphous ITO is then etched away. Due to the selective removal of the amorphous layer during the etching process, the polycrystalline regions remain unaffected. This method thus produces a structured polycrystalline ITO layer.
  • EP 1589579 A2 shows a method for structuring an ITO electrode on a passive matrix display.
  • the OLED-based passive matrix display is structured in one step, in which the ITO layer is combined with the overlying, organic layer
  • Edge jams or the debris pierce the semiconductive layer. This can lead to short circuits and component failure. Therefore edge edgings must be avoided by selecting suitable process windows for these processes. The debris has to go through
  • the object of the present invention is to provide a method for structuring a
  • Layer regions whose or their conductivity is set irradiated with energetic radiation, preferably with laser radiation.
  • a beam intensity below the ablation threshold of the layer material and below a threshold of the layer material is selected, in which the layer between and / or next to the layer regions to be insulated by a modification of the layer material electrically insulating properties receives or in which the one or more layer regions whose or whose conductivity is to be adjusted specifically, obtained by a modification of the layer material, the conductivity to be set.
  • the modification takes place by introducing case states for free charge carriers (electrons or holes) into the layer material and / or by dissolving out dopants, which lead to free charge carriers in the layer material. Under a specific adjustment of the conductivity is the
  • Dot dopants are generally understood to mean atoms or parts of molecules which supply free charge carriers.
  • these can be electron acceptors that are free
  • the dissolution of the dopants is preferably carried out in intrinsically semiconducting materials as well as in organic conductors, for example in TCOs (for example ITO) or organic semiconductors, which are distinguished by specific
  • Molecule parts are doped.
  • trap states are preferred, for example in the form of impurities, lattice defects or grain boundaries
  • Layer or layer areas are removed, which are isolated or their conductivity adjusted.
  • the dopants can either escape from the layer, so that they no longer in the
  • Sample containing the irradiated layer areas are, or are shifted in the layer
  • Dislocation so that largely undoped areas or areas with reduced doping remain.
  • the dislocation of the dopants for example, in inorganic semiconductors and organic
  • the proposed method is thus based on the local modification of the layer material by means of energetic radiation, in particular laser radiation.
  • the electrically conductive or semiconducting layer for example an organic layer or a TCO layer, is irradiated below its removal threshold, so that no removal of material takes place by the irradiation.
  • the irradiation also takes place below the threshold, i. there is no melting of the layer by the irradiation.
  • irradiated layer region still has a conductivity, so that adjacent to the irradiated layer region layer areas are not isolated from each other.
  • the conductivity of the irradiated layer region is above 0.004 S / cm.
  • the adjustment of the conductivity to a predetermined to understand the conductivity value or range. In this case, preference is given to parameters of the energetic radiation, for example pulse number per position,
  • Pulse energy, fluence, wavelength and pulse duration chosen such that the conductivity of the irradiated layer region compared to in the lateral direction, i. Although in the layer direction, adjacent layer areas reduced but not destroyed.
  • the penetration depth of the energetic radiation which may be dependent on wavelength, irradiation duration, dose, number of pulses per position and / or fluence, to be smaller than the layer thickness.
  • the irradiated layer region is not modified over the entire layer thickness, but only over a depth that is smaller than the layer thickness, so that the layer region is not completely deactivated / isolated, but retains a specifically adjustable via the penetration depth conductivity.
  • the number or the density of the introduced case states or of the dissolved-out dopants and thus a conductivity of the irradiated layer region can be influenced in a targeted manner by irradiating the layer and / or the one or more layer regions under predetermined atmospheric conditions For example, a certain process gas atmosphere, a pressure of the atmosphere, the chemical effect of
  • Atmosphere e.g. reducing or oxidizing
  • Atmosphere or a treatment of the layer under liquid is selected.
  • the energy input required in each case for both variants of structuring depends on the layer material and can easily be determined by preliminary experiments with different energies or intensities of the energetic beam and irradiation times.
  • the radiation is pulsed for the irradiation
  • Laser radiation used, wherein the local modification can be done both with a single laser pulse as well as with a sequence of laser pulses.
  • the pulse durations are preferably in the nanosecond range or at even shorter pulse durations. However, longer pulses or cw laser radiation can also be used.
  • the proposed method thus either produces smaller electrically conductive or semiconducting layers
  • Regions understood from a larger layer region of an electrically conductive or semiconducting layer which are separated from each other via electrically insulating regions, or the generation of smaller electrically conductive or semiconducting regions with specifically set or modified, in particular reduced, conductivity understood.
  • the method can be used to isolate several electrically conductive or semiconductive layer areas from one another. Even an electrical isolation of only a single layer area is possible. Both methods can also be used side by side in a layer, i. in a part of the layer becomes the
  • Conductivity is destroyed (insulation) and in another part of the layer, the conductivity is targeted
  • a modification of the layer material is a change in the solid state structure and / or the chemical composition of the layer material
  • the erosion threshold denotes the limit intensity of the energetic beam, from which a removal of the layer material by the beam occurs.
  • the wavelength of the laser radiation preferably used for the irradiation is preferably in the ultraviolet ray range, particularly preferably at a wavelength of ⁇ 300 nm, but may also be at other wavelengths, i. in the visible or infrared
  • Wavelength depends on the respective
  • Electrically insulating properties are understood as meaning an electrical conductivity of ⁇ 0.004 S / cm.
  • Wavelengths of> 300 nm are particularly advantageous for structuring ITO layers or PEDOT: use PSS layers.
  • the method is not based on these layer materials or on transparent
  • the semiconducting properties of organic semiconductors can also be destroyed by the proposed irradiation below the erosion threshold or can be selectively changed or adjusted, in particular reduced, with respect to the conductivity.
  • TCOs eg ITO
  • an increase of the conductivity can be achieved. in this connection the number of trap states at the grain boundaries is reduced.
  • the responsible for the semiconductor properties ⁇ -electron systems are destroyed. Individual regions of an organic semiconductor layer can thus be isolated from one another, whereby the unwanted cross-talk is avoided.
  • bonds are broken in the modification, parts of the molecule dissociate and the layer escapes.
  • inorganic layers there is a dislocation of the electrical
  • electron acceptors can be introduced into an n-conducting layer of electron acceptors or into a p-conducting layer by thermal diffusion during irradiation from the gas phase, which act as additional trap states.
  • the irradiation can also be done with laser radiation different laser or wavelengths simultaneously or immediately after each other. Also, this can reduce the electrical conductivity to form the insulating properties.
  • the proposed method becomes a
  • the proposed method avoids both edge drops and debris consisting of erosion products. This makes it possible to dispense with a subsequent cleaning step. Since the structuring is carried out by means of modification below the removal threshold of the layer material, a lower pulse energy than for the removal of the layer is required. This offers the advantage that the proposed modification by means of energetic or laser radiation can be done much faster than a removal by means of laser radiation.
  • the layer can be processed to a high degree in parallel by splitting laser pulses of high pulse energy into a plurality of partial beams by diffractive optical elements, through which a simultaneous modification of different layer areas can then take place.
  • individual pulse can be structured, increased by the proposed method of pure modification by more than a factor of 10 compared to the area that would be required for a removal of the corresponding areas.
  • the scaling of the surface is possible by a simple change of the imaging ratio in the mask projection. Furthermore, the resolution of the structures produced can also be achieved
  • Another preferred embodiment involves beam deflection by means of fast scanners. Under a fast scanner becomes here a system
  • a wavelength of the energetic radiation is selected such that its penetration depth is greater than a layer thickness of the layer. This ensures a modification of the layer over the entire layer thickness. If the penetration depth is chosen smaller than the layer thickness, the layer can not be completely deactivated or isolated.
  • a conductivity gradient or conductivity profile is generated in a section of the layer by varying at least one parameter of the energetic radiation.
  • the at least one parameter is selected from a group of parameters that includes number of pulses per point, pulse energy, fluence, wavelength and pulse duration.
  • the conductivity profile can be adjusted in the vertical and / or in the lateral direction of the layer.
  • the conductivity profile in the lateral direction, ie in the layer direction can be, for example, stepped by stepwise variation of at least one parameter or gradually by continuous change
  • At least one parameter of the energetic radiation can be adjusted.
  • a conductivity gradient or course can be achieved, for example, by irradiating the section of the layer in the lateral direction with energy radiation of different penetration depth, so that the modified regions reach different depths.
  • the conductivity gradient or course in the lateral direction can also be achieved by varying the
  • Parameters e.g. Fluence, number of pulses per site, the number or density of the trap states or of the released dopants is varied.
  • the inventive method thus allows in this embodiment, the targeted and flexible adjustment of the conductivity. In this way, in the operation of the electrically conductive or semiconducting layer, the local
  • the method can therefore be used particularly advantageously for this purpose, for example by being transparent
  • Modification for example, can also be achieved by means of electron beam machining. However, this processing must be performed in contrast to the processing with laser radiation in a vacuum.
  • the proposed method can be used above all in thin-film electronics, in particular in large-scale, organic electronics. In these areas of electronics, individual thin layers with different electrical properties are used. The individual layers must be structured according to their application.
  • Fig. 1 is a schematic representation of
  • Fig. 2 is a comparison of the structuring of
  • Fig. 3 is a schematic representation of a
  • an electrically conductive or semiconducting layer is structured such that electrically conductive regions of a specific geometry, for example, conductor tracks or the
  • FIG. 1 shows a highly schematic example of an implementation of the proposed method. In the figure is a
  • Substrate 2 to recognize, for example, a glass substrate on which a corresponding electrically conductive layer 1 is applied.
  • This layer may, for example, be an ITO layer or a PEDOT: PSS layer
  • this layer 1 in the present example with a laser beam 3 of a Lasers 4 irradiated, which is guided via a scanning device 5 over the areas to be irradiated.
  • the corresponding optics, in particular the focusing optics for the laser beam 3, are not shown here.
  • the laser intensity is chosen in each case so that no material removal takes place, but the layer material is modified so that the electrical conductivity or the semiconductor properties of the layer 1 in the irradiated areas are destroyed. So the electrical conductivity is in one
  • ITO layer for example.
  • the electrical conductivity of a layer of the organic conductor PEDOT: PSS is modified by the irradiation by means of individual pulses of wavelengths less than 300 nm below the erosion threshold so that it is destroyed.
  • the optical penetration depth of the radiation must be greater than the layer thickness, so that the layer is modified in its full thickness.
  • this can be achieved, for example, with laser pulses having a wavelength of 248 nm.
  • FIG. 2 shows a schematic representation of a comparison of the known laser structuring by means of material removal in partial image a) with the proposed method in partial image b), in which the laser structuring takes place by means of material modification. From the figure it can be seen that in the previous technique of laser structuring by means of material removal at the edges of the electrically conductive regions 6, undesired edge drops 8 occur. Furthermore, unwanted deposits of debris 7 on the surface of the electric
  • Layer region 9 between the electrically conductive layer regions 6 generates, which is electrically insulating. Thus, there is no layer removal and also no removal of the layer material between the electrically conductive regions 6, for example by etching.
  • FIG. 3 shows an example of a plan view of a section of a correspondingly structured layer region, for example for producing parallel, electrically transparent electrodes on a glass substrate.
  • the electrically conductive regions 6 can be seen, which form the electrodes and modified by the corresponding
  • Layer regions 9 are electrically isolated from each other. Such processing of parallel areas can, for example, by mask projection of a corresponding

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Laser Beam Processing (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne la structuration d'une couche électriquement conductrice ou semi-conductrice qui permet d'isoler électriquement une ou plusieurs zones (6) de la couche et/ou d'ajuster la conductivité électrique d'une ou plusieurs zones de la couche de manière ciblée. Dans le procédé, entre les zones (6) de la couche à isoler et/ou à côté de celles-ci, la couche est irradiée localement par un rayonnement énergétique. En variante, les une ou plusieurs zones de la couche, dont la conductivité doit être ajustée de façon ciblée, sont irradiées par le rayonnement énergétique. Pour irradier la couche, on choisit une intensité de rayonnement qui est inférieure au seuil d'abrasion du matériau de la couche et inférieure à un seuil de fusion du matériau de la couche et pour laquelle une modification du matériau de la couche confère à la couche des propriétés d'isolation électrique ou de conductivité électrique sélectivement réduite. La modification se fait par l'introduction d'états de diminution de porteurs de charge libres dans le matériau de la couche ou par l'extraction de dopants pour les porteurs de charge libres du matériau de la couche.
PCT/EP2014/002091 2013-08-01 2014-07-30 Procédé de structuration d'une couche électriquement conductrice ou semi-conductrice Ceased WO2015014489A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013012730.0A DE102013012730B4 (de) 2013-08-01 2013-08-01 Verfahren zur Strukturierung einer elektrisch leitenden oder halbleitenden Schicht
DE102013012730.0 2013-08-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016146695A1 (fr) * 2015-03-19 2016-09-22 Osram Oled Gmbh Procédé de fabrication d'un substrat pour un composant électroluminescent et composant optoélectronique organique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020058366A1 (en) * 2000-06-12 2002-05-16 Seiko Epson Corporation Thin-film semiconductor device fabrication method
US6930009B1 (en) * 1995-12-05 2005-08-16 Nathaniel R. Quick Laser synthesized wide-bandgap semiconductor electronic devices and circuits
EP1589579A2 (fr) * 2004-04-22 2005-10-26 Hewlett-Packard Development Company, L.P. Methode de formation de motifs d'une diode organique electroluminescente
US20100105196A1 (en) * 2008-10-24 2010-04-29 Industrial Technology Research Institute Method for patterning polycrystalline indium tin oxide
WO2011007297A2 (fr) * 2009-07-16 2011-01-20 Koninklijke Philips Electronics N.V. Procédé de production de couches conductrices structurées
US20120231588A1 (en) * 2011-03-10 2012-09-13 Shin-Chuan Chiang Manufacturing method of thin film transistor
US20130005139A1 (en) * 2011-06-30 2013-01-03 Guardian Industries Corp. Techniques for manufacturing planar patterned transparent contact and/or electronic devices including same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6930009B1 (en) * 1995-12-05 2005-08-16 Nathaniel R. Quick Laser synthesized wide-bandgap semiconductor electronic devices and circuits
US20020058366A1 (en) * 2000-06-12 2002-05-16 Seiko Epson Corporation Thin-film semiconductor device fabrication method
EP1589579A2 (fr) * 2004-04-22 2005-10-26 Hewlett-Packard Development Company, L.P. Methode de formation de motifs d'une diode organique electroluminescente
US20100105196A1 (en) * 2008-10-24 2010-04-29 Industrial Technology Research Institute Method for patterning polycrystalline indium tin oxide
WO2011007297A2 (fr) * 2009-07-16 2011-01-20 Koninklijke Philips Electronics N.V. Procédé de production de couches conductrices structurées
US20120231588A1 (en) * 2011-03-10 2012-09-13 Shin-Chuan Chiang Manufacturing method of thin film transistor
US20130005139A1 (en) * 2011-06-30 2013-01-03 Guardian Industries Corp. Techniques for manufacturing planar patterned transparent contact and/or electronic devices including same

Non-Patent Citations (1)

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Title
ITOH E ET AL: "Excimer-laser micropatterned photobleaching as a means of isolating polymer electronic devices", SYNTHETIC METALS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 156, no. 2-4, 1 February 2006 (2006-02-01), pages 129 - 134, XP027940231, ISSN: 0379-6779, [retrieved on 20060201] *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016146695A1 (fr) * 2015-03-19 2016-09-22 Osram Oled Gmbh Procédé de fabrication d'un substrat pour un composant électroluminescent et composant optoélectronique organique

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DE102013012730A1 (de) 2015-02-05
DE102013012730B4 (de) 2018-09-20

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