US20090126787A1 - Solar cell and an arrangement and a method for producing a solar cell - Google Patents

Solar cell and an arrangement and a method for producing a solar cell Download PDF

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Publication number
US20090126787A1
US20090126787A1 US12/280,602 US28060207A US2009126787A1 US 20090126787 A1 US20090126787 A1 US 20090126787A1 US 28060207 A US28060207 A US 28060207A US 2009126787 A1 US2009126787 A1 US 2009126787A1
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Prior art keywords
solar cell
layer
surface area
coating
area
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US12/280,602
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English (en)
Inventor
Jari Ruuttu
Reijo Lappalainen
Vesa Myllymaki
Lasse Pulli
Juha Makitalo
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Picodeon Ltd Oy
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Picodeon Ltd Oy
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Priority claimed from FI20060181A external-priority patent/FI20060181L/fi
Priority claimed from FI20060178A external-priority patent/FI20060178L/fi
Priority claimed from FI20060177A external-priority patent/FI20060177L/fi
Priority claimed from FI20060182A external-priority patent/FI20060182L/fi
Priority claimed from FI20060357A external-priority patent/FI124239B/fi
Application filed by Picodeon Ltd Oy filed Critical Picodeon Ltd Oy
Assigned to PICODEON LTD OY reassignment PICODEON LTD OY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LAPPALAINEN, REIJO, MYLLYMAKI, VESA, MAKITALO, JUHA, PULLI, LASSE, RUUTTU, JARI
Publication of US20090126787A1 publication Critical patent/US20090126787A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/08—Devices involving relative movement between laser beam and workpiece
    • B23K26/082—Scanning systems, i.e. devices involving movement of the laser beam relative to the laser head
    • B23K26/0821—Scanning systems, i.e. devices involving movement of the laser beam relative to the laser head using multifaceted mirrors, e.g. polygonal mirror
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates generally to solar cells, material layers within solar cells, a production method of solar cells, and a manufacturing arrangement for producing solar cells. More specifically, the present invention relates to what is disclosed in the preamble of the independent claim.
  • Solar cells provide an ecological way of producing energy, and they have therefore been under intensive development.
  • Solar cells are generally made of photovoltaic cells.
  • a photovoltaic cell has a at least one semiconducting layer, wherein photons of light are absorbed. The absorption of light causes electrons or holes to transfer to a higher, conducting energy level, and this energy can be used as electricity.
  • a solar cell In order to conduct the formed electricity out of the solar cells there must be a conducting layer at the both sides of the semiconducting layer(s).
  • the conducting layer at the radiated surface of the solar cell must allow light to enter the semiconductor layer.
  • a solar cell is usually partitioned into small cells which are connected in series or parallel. In this case the conducting layers and possibly the semiconductor layer(s) are patterned to provide the required circuitry.
  • the radiated surface of the solar cell is further coated with one or several layers for providing antireflection surface for the solar cell, and for protecting the solar cell from mechanical, chemical and physical stresses of the environment.
  • Such surfaces may be radiation stabilized glass or plastic products.
  • a glass layer may include self-cleaning TiO 2 coating made by sputtering, Hot-Aerosol-Layering-Operation (nHALO) and by ALD-techniques.
  • the outermost protecting layers may be integrated in the solar cell or they can be separated from the electrical layers.
  • the substrate may be e.g. glass or plastic.
  • the substrate can be used as the radiated surface of the solar cell, in which case the substrate is made transparent.
  • the solar cells made with this technology have less weight and are not as sensitive to mechanical stresses. However, it has been a problem to achieve sufficient efficiency; usually less than 10% of the energy of light can be converted into electrical energy.
  • One reason for this is the non-homogeneity of the produced layers. Therefore the transparency of the radiated layers may be insufficient. Also, the non-homogeneity of semiconducting layers causes loss of energy.
  • a junction of semiconducting layer has a specified electric potential threshold, and the energy of photons can only be converted into an amount of energy which corresponds to the potential threshold.
  • the solar light has a wide spectrum of wavelengths and thus the photons have a wide range of energies. If the energy of a photon is lower than the threshold potential of the semiconducting junction, the photon is not converted into electrical energy. On the other hand, if the energy of a photon is higher than the threshold potential of the semiconducting junction, the photon is converted into energy according to the potential threshold, but the energy of the photon above the threshold is converted into heat.
  • the problem of converting wide spectrum radiation into electrical energy could be solved by providing several successive, transparent semiconductor layers wherein each pair of semiconducting layers provides a junction for converting light to electricity.
  • the semiconductor junctions nearest to the radiated surface have the highest threshold potential and the threshold potential decreases when the radiation enters the following junctions. This way a photon is converted into electricity at a junction which has a threshold potential close to the photon energy, and high efficiency could be achieved.
  • the above mentioned problems become all much more difficult when producing large solar cells as it is necessary to produce layers of large surfaces.
  • the known technologies are suitable for producing cells of small dimensions, e.g. areas of a few cm 2 at the most, but the quality of surfaces and homogeneity of materials become worse if known technologies would be applied in producing solar cells with layers of large surfaces.
  • the applicant has investigated possibilities for using laser cold ablation in production of solar cells.
  • considerable development of the laser technology has provided means to produce very high-efficiency laser systems that are based on semi-conductor fibres, thus supporting advance in so called cold ablation methods.
  • Cold ablation is based on forming high energy laser pulses of short duration, such as within picosecond range, and directing the pulses into the surface of a target material. A plume of plasma is thus ablated from the area where the laser beam hits the target.
  • the applications of cold ablation include e.g. coating and machining.
  • both qualitative and production rate related problems associated with coating, thin film production as well as cutting/grooving/carving etc. has been approached by focusing on increasing laser power and reducing the spot size of the laser beam on the target. However, most of the power increase was consumed to noise. The qualitative and production rate related problems were still remaining although some laser manufacturers resolved the laser power related problem. Representative samples for both coating/thin film as well as cutting/grooving/carving etc. could be produced only with low with repetition rates, narrow scanning widths and with long working time beyond industrial feasibility as such, highlighted especially for large bodies.
  • the pulse duration decrease further to femto or even to atto-second scale makes the problem almost irresolvable.
  • the pulse energy should be 5 ⁇ J for a 10-30 ⁇ m spot, when the total power of the laser is 100 W and the repetition rate 20 MHz.
  • Such a fibre to tolerate such a pulse is not available at the priority date of the current application according to the knowledge of the writer at the very date.
  • the prior art laser treatment systems most often include optical scanners which are based on vibrating mirrors.
  • Such an optical scanner is disclosed in e.g. document DE10343080.
  • a vibrating mirror oscillates between two determined angles relative to an axis which is parallel to the mirror.
  • the vibrating mirror thus reflects or “scans” the laser beam into points of a line at the surface of a target material.
  • FIG. 1 a An example of a vibrating scanner or “galvano-scanner” is illustrated in FIG. 1 a . It has two vibrating mirrors, one of which scans the beam relative to X-axis and another scans the beam relative to orthogonal y-axis.
  • the production rate is directly proportional to the repetition rate or repetition frequency.
  • the known mirror-film scanners galvano-scanners or back and worth wobbling type of scanners
  • the stopping of the mirror at the both ends of the duty cycle is somewhat problematic as well as the accelerating and decelerating related to the turning point and the related momentary stop, which all limit the usability of the mirror as scanner, but especially also to the scanning width.
  • the present coating methods employing galvano-scanners can produce scanning widths at most 10 cm, preferably less. If the production rate were tried to be scaled up, by increasing the repetition rate, the acceleration and deceleration cause either a narrow scanning range, or uneven distribution of the radiation and thus the plasma at the target when radiation hit the target via accelerating and/or decelerating mirror.
  • the target may not only ware out unevenly but may also fragment easily and degrade the plasma quality.
  • the surface to be coated with such plasma also suffers the detrimental effects of the plasma.
  • the surface may comprise fragments, plasma may be not evenly distributed to form such a coating etc. which are problematic in accuracy demanding application, but may be not problematic, with paint or pigment for instance, provided that the defects keep below the detection limit of the very application.
  • the present methods ware out the target in a single use so that same target is not available for a further use from the same surface again.
  • the problem has been tackled by utilising only a virgin surface of the target, by moving target material and/or the beam spot accordingly.
  • the left-overs or the debris comprising some fragments also can make the cut-line uneven and thus inappropriate, as the case could for instance in flow-control drillings.
  • the surface could be formed to have a random bumpy appearance caused by the released fragments, which may be not appropriate in manufacturing of solar cells.
  • the mirror-film scanners moving back and forth generate inertial forces that load the structure it self, but also to the bearings to which the mirror is attached and/or which cause the mirror movement.
  • Such inertia little by little may loosen the attachment of the mirror, especially if such mirror were working nearly at the extreme range of the possible operational settings, and may lead to roaming of the settings in long time scale, which may be seen from uneven repeatability of the product quality.
  • Because of the stoppings, as well as the direction and the related velocity changes of the movement, such a mirror-film scanner has a very limited scanning width so to be used for ablation and plasma production.
  • the effective duty cycle is relatively short to the whole cycle, although the operation is anyway quite slow.
  • the plasma making rate is in prerequisite slow, scanning width narrow, operation unstable for long time period scales, but yield also a very high probability to get involved with unwanted particle emission in to the plasma, and consequently to the products that are involved with the plasma via the machinery and/or coating.
  • the product lifetime of solar cells should also be increased and the maintenance costs should be lowered, sustainable development being a prerequisite.
  • FIGS. 2 a and 2 b Plasma related quality problems are demonstrated in FIGS. 2 a and 2 b , which indicate plasma generation according to known techniques.
  • a laser pulse 214 hits a target surface 211 .
  • the depth h and the beam diameter d are of the same magnitude, as the heat of the pulse 214 also heat the surface at the hit spot area, but also beneath the surface 211 in deeper than the depth h.
  • the structure experiences thermal shock and tensions are building, which while breaking, produce fragments illustrated F.
  • the plasma may be in the example quite poor in quality, there appears to be also molecules and clusters of them indicate by the small dots 215 , as in the relation to the reference by the numeral 215 for the nuclei or clusters of similar structures, as formed from the gases 216 demonstrated in the FIG.
  • the letter “o”s demonstrate particles that can form and grow from the gases and/or via agglomeration.
  • the released fragments may also grow by condensation and/or agglomeration, which is indicated by the curved arrows from the dots to Fs and from the os to the Fs.
  • Curved arrows indicate also phase transitions from plasma 213 to gas 216 and further to particles 215 and increased particles 217 in size.
  • the ablation plume in FIG. 2 b can comprise fragments F as well as particles built of the vapours and gases, because of the bad plasma production, the plasma is not continuous as plasma region, and thus variation of the quality may be met within a single pulse plume.
  • the target surface 211 in FIG. 2 b is not any more available for a further ablations, and the target is wasted, although there were some material available.
  • An object of the present invention is to provide solar cells, as well as an arrangement and method of their production, wherein the described disadvantages of the prior art are avoided or reduced.
  • the object of the invention is therefore to provide a technology for producing layers with certain surface by pulsed laser deposition that so that the uniform surface area to be coated comprises at least 0.2 dm 2 .
  • a second object of this invention is to provide new solar cell products wherein layers are produced by pulsed laser deposition so that the uniform surface area of the layer comprises an area of at least at least 0.2 dm 2 .
  • a third object of this invention is to solve a problem how to provide available such fine plasma practically from a target to be used in solar cell products, so that the target material do not form into the plasma any particulate fragments either at all, i.e. the plasma is pure plasma, or the fragments, if exist, are rare and at least smaller in size than the ablation depth to which the plasma is generated by ablation from said target.
  • a fourth object of the invention is to provide at least a new method and/or related means to solve how to provide the uniform surface area of a layer in a solar cell product with the high quality plasma without particulate fragments larger in size than the ablation depth to which the plasma is generated by ablation from said target, i.e. to coat substrates with pure plasma.
  • a fifth object of this invention is to is to provide a good adhesion of the coating to the uniform surface area of a glass product by said pure plasma, so that wasting the kinetic energy to particulate fragments is suppressed by limiting the existence of the particulate fragments or their size smaller than said ablation depth. Simultaneously, the particulate fragments because of their lacking existence in significant manner, they do not form cool surfaces that could influence on the homogeneity of the plasma plume via nucleation and condensation related phenomena.
  • a sixth object of the invention is to provide at least a new method and/or related means to solve a problem how to provide a broad scanning width simultaneously with fine plasma quality and broad coating width even for large solar cell bodies in industrial manner.
  • a seventh object of the invention is to provide at least a new method and/or related means to solve a problem how to provide a high repetition rate to be used to provide industrial scale applications in accordance with the objects of the invention mentioned above.
  • An eighth object of the invention is to provide at least a new method and/or related means to solve a problem how to provide good quality plasma for coating of uniform glass surfaces to manufacture solar cell products according to the first to seven objects, but still save target material to be used in the coating phases producing same quality coatings/thin films where needed.
  • a further object of the invention is to use such method and means according previous objects to solve a problem how to cold-work and/or produce layers of a solar cell.
  • the present invention is based on the surprising discovery that layers for solar cell products comprising large surfaces can be produced with industrial production rates and excellent qualities regarding one or more of technical features such as optical transparency, chemical and/or wear resistance, scratch-free-properties, thermal resistance and/or conductivity, resistivity, coating adhesion, self-cleaning properties, particulate-free coatings, pinhole-free coatings and electronic conductivity by employing ultra short pulsed laser deposition in a manner wherein pulsed laser beam is scanned with a rotating optical scanner comprising at least one mirror for reflecting said laser beam.
  • the present method accomplishes the economical use of target materials, because they are ablated in a manner accomplishing the reuse of already subjected material with retained high coating results.
  • the present invention further accomplishes the producing of product layers in low vacuum conditions with simultaneously high coating properties. Moreover, the required coating chamber volumes are dramatically smaller than in competing methods. Such features decrease dramatically the overall equipment cost and increase the coating production rate. In many preferable cases, the coating equipment can be fitted into production-line in online manner.
  • the object of the invention is achieved by providing a method for producing by laser ablation at least one layer having a surface and to be used as part of a solar cell, which is characterized in that the surface area to be produced comprises at least an area 0.2 dm 2 and the coating is performed by employing ultra short pulsed laser deposition wherein pulsed laser beam is scanned with a rotating optical scanner comprising at least one mirror for reflecting said laser beam.
  • the invention also relates to a solar cell comprising at least one layer with a surface, produced by laser ablation, which is characterized in that the uniform surface area to be produced comprises at least an area 0.2 dm 2 and the layer has been produced by employing ultra short pulsed laser deposition wherein pulsed laser beam is scanned with a rotating optical scanner comprising at least one mirror for reflecting said laser beam.
  • light means any electromagnetic radiation which can be used for cold ablation and “laser” means light which is coherent or a light source producing such light. “Light or “laser” is thus not restricted in any way to the visible part of the light spectrum.
  • ultra short pulse laser deposition means that a certain point at the target surface is radiated with a laser beam for a time period of less than 1 ns, preferably less than 100 ps at a time. Such an exposure may be repeated at the same location of the target.
  • coating means forming material layer of any thickness on a substrate. Coating thus may also mean producing thin films with a thickness of e.g. ⁇ 1 ⁇ m.
  • surface may mean surface of a layer, coating and/or, wherein the surface may be an outer surface or it may form an interface with other layer/coating/substrate.
  • the surface may also be a surface of a half-finished product, which may be further processed to achieve a final product.
  • FIG. 1 illustrates an exemplary galvano-scanner set-up employed in state of the art cold ablation coating/thin-film production and in machining and other work-related applications.
  • FIG. 1 b illustrates the situation wherein prior art galvanometric scanner is employed in scanning laser beam resulting in heavy overlapping of pulses with repetition rate of 2 Mhz.
  • FIG. 2 a illustrates plasma-related problems of known techniques.
  • FIG. 2 b illustrates further plasma-related problems of known techniques.
  • FIG. 3 illustrates exemplary layers produced for a solar cell.
  • FIG. 4 illustrates an exemplary arrangement according to the invention for producing a layer for a solar cell using pulsed laser technology.
  • FIG. 5 illustrates an exemplary arrangement according to the invention for producing several layers of a solar cell using pulsed laser technology.
  • FIG. 6 a illustrates one possible turbine scanner mirror employed in a method according to the invention
  • FIG. 6 b illustrates the movement of the ablating beam achieved by each mirror in the example of FIG. 6 a.
  • FIG. 7 illustrates beam guidance through one possible rotating scanner to be employed according to the invention.
  • FIG. 8 a illustrates beam guidance through another possible rotating scanner to be employed according to the invention.
  • FIG. 8 b illustrates beam guidance through a further possible rotating scanner to be employed according to the invention.
  • FIG. 10 a illustrates an embodiment according to the invention, wherein target material ablated by scanning the laser beam with rotating scanner (turbine scanner).
  • FIG. 10 b illustrates an exemplary part of target material of FIG. 10 a.
  • FIG. 10 c illustrates an exemplary ablated spot of target material of FIG. 110 b.
  • FIG. 11 illustrates an exemplary way according to the invention to scan and ablate target material with a rotating scanner.
  • FIGS. 1 a , 1 b , 2 a and 2 b where already described above in the prior art description.
  • FIG. 3 illustrates exemplary layers of a solar cell, which is based on film layer technology.
  • the substrate 360 may be e.g. glass or plastic material.
  • a antireflection layer 362 At the radiated surface of the solar cell there is a antireflection layer 362 . There may also be other or additional layers for keeping the outer surface clean and protected from environmental stresses.
  • an electrically conducting layer 364 At the inner surface of the substrate 360 there is an electrically conducting layer 364 which may be patterned according to the circuit layout and partitioning of the solar cell.
  • the conducting layer is preferably transparent and/or the conductive wiring is made of narrow leads which cover only a small part of the surface area.
  • the conductive layer there is one or several semiconducting layers 366 .
  • the second conductive layer need not be transparent if there are no further semiconducting layers behind the conducting layer. There may also be an additional, protecting layer at the surface of the second conductive layer.
  • FIG. 4 illustrates an exemplary system for treating material with laser ablation.
  • the target 47 has a form of a band which is spooled from a feed roll 48 into a discharge roll 46 .
  • the target is supported with a support plate 51 which has an opening 52 at the location of ablation.
  • the target may alternatively be other than band, such as a rotating cylinder of target material.
  • the laser beam 49 received from the scanner hits the target, material is ablated, and a plasma plume is provided.
  • a substrate 50 is provided into the plasma plume. The substrate will thus be coated with a layer of target material. If a layer is to be machined after the deposition, this can be made with a laser beam.
  • the laser ablation with many other alternative structures and arrangements.
  • target material which is provided on a transparent sheet.
  • the target sheet can be first produced by ablating the target material on a transparent sheet.
  • FIG. 5 illustrates an exemplary production line arrangement for producing layers for a solar cell.
  • the arrangement includes five laser processing units 571 - 575 within a same processing chamber 510 .
  • Above the processing unit there is a conveyor 591 for transferring substrates 581 - 585 along the line.
  • Each processing unit provides a certain process for the substrate.
  • the processing units may produce layers or they may provide laser machining of the substrate or produced layers.
  • a method for providing a layer for a solar cell with a certain surface by laser ablation in which method the surface area to be coated comprises at least 0.2 dm 2 and the depositing is carried by employing ultra short pulsed laser deposition wherein pulsed laser beam is scanned with a rotating optical scanner comprising at least one mirror for reflecting said laser beam.
  • Ultra Short Laser Pulsed Deposition is often shortened USPLD.
  • Said deposition is also called cold ablation, in which one of the characteristic features is that opposite for example to competing nanosecond lasers, practically no heat transfer takes place from the exposed target area to the surroundings of this area, the laser pulse energies being still enough to exceed ablation threshold of target material.
  • the pulse lengths are typically under 50 ps, such as 5-30 ps. i.e. ultra short, the phenomena of cold ablation being reached with pico-second but also femto-second and atto-second pulsed lasers.
  • the material evaporated from the target by laser ablation is deposited onto a substrate that can be held near room temperature. Still, the plasma temperature reaches 1,000,000 K on exposed target area.
  • said uniform surface area comprises at least 0.5 dm 2 . In a still more preferred embodiment of the invention, said uniform surface area comprises at least 1.0 dm 2 .
  • the invention accomplishes easily also the coating of products comprising uniform coated surface areas larger than 0.5 m 2 , such as 1 m 2 and over. The process is especially beneficial for coating large surfaces of layers for solar cells with high quality plasma.
  • the intensity of laser pulses In industrial applications, it is important to achieve high efficiency of laser treatment. In cold ablation, the intensity of laser pulses must exceed a predetermined threshold value in order to facilitate the cold ablation phenomenon. This threshold value depends on the target material. In order to achieve high treatment efficiency and thus, industrial productivity, the repetition rate of the pulses should be high, such as 1 MHz, preferably over 2 MHz and more preferably over 5 MHz. As mentioned earlier, it is advantageous not to direct several pulses into same location of the target surface because this causes a cumulating effect in the target material, with particle deposition leading to bad quality plasma and thus, bad quality coatings and thin-films, undesirable eroding of the target material, possible target material heating etc.
  • the velocity of the beam at the surface of the target should generally be more than 10 m/s to achieve efficient processing, and preferably more than 50 m/s and more preferably more than 100 m/s, even such speeds as 2000 m/s.
  • FIG. 6 a illustrates an example of a rotating turbine scanner, which can be used in implementing the invention.
  • rotating optical scanner comprises at least three mirrors for reflecting laser beam.
  • in the coating method employs a polygonal prism illustrated in FIG. 5 .
  • a polygonal prism has faces 21 , 22 , 23 , 24 , 25 , 26 , 27 and 28 .
  • Arrow 20 indicates that the prism can be rotated around its axis 19 , which is the symmetry axis of the prism.
  • FIG. 6 a are mirror faces, advantageously oblique in order to achieve scanning line, arranged such that each face in its turn will change, by means of reflection, the direction of radiation incident on the mirror surface as the prism is rotated around its axis, the prism is applicable in the method according to an embodiment of the invention, in its radiation transmission line, as part of a rotating scanner, i.e. turbine scanner.
  • FIG. 6 a shows 8 faces, but there may be considerably more faces than that, even dozens or hundreds of them.
  • FIG. 6 a also shows that the mirrors are at the same oblique angle to the axis, but especially in an embodiment including several mirrors, the said angle may vary in steps so that, by means of stepping within a certain range, a certain stepped shift on the work spot is achieved on the target, illustrated in FIG. 6 b .
  • the different embodiments of invention are not to be limited into various turbine scanner mirror arrangements regarding for example the size, shape and number of laser beam reflecting mirrors.
  • the structure of the turbine scanner, FIG. 6 a includes at least 2 mirrors, preferably more than 6 mirrors, e.g. 8 mirrors ( 21 to 28 ) positioned symmetrically around the central axis 19 .
  • the mirrors direct the radiation, a laser beam, for instance, reflected from spot 29 , accurately onto the line-shaped area, always starting from one and the same direction ( FIG. 6 b ).
  • the mirror structure of the turbine scanner may be non-tilted ( FIG. 7 ) or tilted at a desired angle, e.g. FIGS. 8 a and 8 b .
  • the size and proportions of the turbine scanner can be freely chosen. In one advantageous embodiment of the coating method it has a perimeter of 30 cm, diameter of 12 cm, and a height of 5 cm.
  • the mirrors 21 to 28 of the turbine scanner are preferably positioned at oblique angles to the central axis 19 , because then the laser beam is easily conducted into the scanner system.
  • the mirrors 21 to 28 can deviate from each other in such a manner that during one round of rotational movement there are scanned as many line-shaped areas ( FIG. 6 b ) 29 as there are mirrors 21 to 28 .
  • rotating optical is here meant scanners comprising at least one mirror for reflecting laser beam.
  • FIG. 9 illustrates a scanner 910 with one rotating mirror.
  • the mirror 914 is arranged to rotate around the axis of rotation 916 .
  • FIG. 9 also shows the side view and the end view of the mirror.
  • the mirror has a shape of a cylinder, which is slightly tilted in relation to the axis of rotation 916 .
  • the mirror is shown as a tilted cylinder in order to better visualize the form of the mirror, and the ends of the mirror are therefore oblique.
  • edges which are perpendicular to the axis of rotation it would also be possible to have edges which are perpendicular to the axis of rotation.
  • the optical scanner has an axle at the axis of rotation, in which the mirror is connected.
  • the mirror may be connected to the rotating axle with e.g. end plates or spokes (not shown in the Figure).
  • FIG. 10 a demonstrates a target material ablated with pico-second-range pulsed laser employing rotating scanner with speed accomplishing the ablation of target material with slight overlapping of adjacent pulses, avoiding the problems associated with prior art galvano-scanners.
  • FIG. 10 b shows enlarged picture of one part of the ablated material, clearly demonstrating the smooth and controlled ablation of material on both x- and y-axis and thus, generation of high quality, particle-free plasma and further, high quality thin-films and coatings.
  • FIG. 10 c demonstrates one example of possible x- and y-dimensions of one single ablation spot achieved by one or few pulses.
  • the invention accomplishes the ablation of material in a manner wherein the width of the ablated spot is always much bigger than the depth of the ablated spot area.
  • the possible particles could now have a maximum size of the spot depth.
  • the rotating scanner now accomplishes the production of good quality, particle free plasma with great production rate, with simultaneously large scanning width, especially beneficial for substrates comprising large surface areas to be coated.
  • the FIGS. 10 a , 10 b and 10 c clearly demonstrate that opposite to present techniques, the already ablated target material area can be ablated for new generation of high class plasma—reducing thus radically the overall coating/thin-film producing cost.
  • FIG. 11 demonstrates an example wherein coating is carried out by employing a pico-second USPLD-laser and scanning the laser pulses with turbine scanner.
  • the scanning speed is 30 m/s, the laser spot-width being 30 ⁇ m.
  • the layer of conductive transparent material can be made of e.g. indium tin oxide, aluminum doped zinc oxide, tin oxide or fluorine-doped tin oxide.
  • the layer of conductive non-transparent material can be made of e.g. aluminum, copper or silver.
  • the layer of semiconducting material can be made of e.g. silicon, germanium indium tin oxide, aluminum doped zinc oxide, tin oxide or fluorine-doped tin oxide.
  • the layer of antireflective coating can be made of e.g. of silicon nitride or titanium oxide. However, this are just some examples of commonly used materials. Next, some further alternatives are discussed in more detail.
  • Advantageous metal oxides include for example aluminum oxide and its different composites such as aluminum titan oxide (ATO). Due to its resistivity, high-optical transparencies possessing high-quality indium tin oxide (ITO) is especially preferred in applications wherein the coating can be employed to warm-up the coated surface. It can also be employed in solar-control Yttrium stabilized zirconium oxide is another example of different oxides possessing both excellent optical, wear-resistant properties.
  • ATO aluminum titan oxide
  • ITO indium tin oxide
  • Yttrium stabilized zirconium oxide is another example of different oxides possessing both excellent optical, wear-resistant properties.
  • Some further metals can also be applied in solar cell applications.
  • the optical properties of metal-derived thin-films are somewhat different from those of bulk metals.
  • ultrathin films ( ⁇ 100 ⁇ thick) variations make the concept of optical constants problematic, the quality and surface roughness of the coating (thin film) being thus critical technical features.
  • Such coatings can easily be produced with the method of present invention.
  • Dielectric materials employed in present applications include fluorides (e.g. MgF 2 , CeF 3 ), oxides (e.g. Al 2 O 3 , TiO 2 , SiO 2 ), sulfides (e.g. ZnS, CdS) and assorted compounds such as ZnSe and ZnTe.
  • fluorides e.g. MgF 2 , CeF 3
  • oxides e.g. Al 2 O 3 , TiO 2 , SiO 2
  • sulfides e.g. ZnS, CdS
  • ZnSe and ZnTe assorted compounds such as ZnSe and ZnTe.
  • Dielectric coatings can be advantageously
  • Transparent conducting films may consist either of very thin metals or semiconducting oxides and/ and most presently even nitrides such as indium gallium nitride in front electrodes for solar cells.
  • Metals that have conventionally been employed be as transparent conductors include Au, Pt, Rh, Ag, Cu, Fe and Ni. Simultaneous optimization of conductivity and transparency presents a considerable challenge in film deposition. At one extreme are discontinuous islands of considerable transparency but high resistivity; at the other are films that coalesce early and are continuous, possessing high conductivity but low transparency. For these reasons, the semi-conducting oxides such as SnO 2 , In 2 O 3 , CdO, and, more commonly, their alloys (e.g. ITO), doped In 2 O 3 (with Sn, Sb) and doped SnO 2 (with F, Cl, etc.) are used.
  • SnO 2 , In 2 O 3 , CdO and, more commonly, their alloys (e.g. ITO), doped In 2 O 3 (with Sn, Sb) and doped SnO 2 (with F, Cl, etc.
  • the metal oxide coatings can be produced by either ablating metal or metals in active oxygen atmosphere or by ablating oxide-materials. Even in latter possibility, it is possible to enhance the coating quality and/or production rate by conducting the ablation in reactive oxygen.
  • nitrides it is according to the invention possible to use nitrogen atmosphere or liquid ammonia in order to enhance the coating quality.
  • a representative example of invention is production of carbon nitride (C 3 N 4 films).
  • said uniform surface area of solar cell layer is produced with carbon material comprising over 90 atomic-% of carbon, with more than 70% of sp 3 -bonding.
  • carbon material comprising over 90 atomic-% of carbon, with more than 70% of sp 3 -bonding.
  • Such materials include for example amorphous diamond, nano-crystalline diamond or even pseudo-monocrystalline diamond.
  • Various diamond coatings give the glass product excellent tribological, wear- and scratch-free properties but increase also the heat-conductivity and -resistance. Diamond-coatings on glass can be used with special preference in solar cells, if of high quality, i.e. crystalline form.
  • said uniform surface area of may be produced of material comprising carbon, nitrogen and/or boron in different ratios.
  • materials include boron carbon nitride, carbon nitride (both C 2 N 2 and C 3 N 4 ), boron nitride, boron carbide or phases of different hybridizations of B—N, B—C and C—N phases.
  • Said materials are diamond-like materials having low densities, are extremely wear-resistant, and are generally chemically inert.
  • carbon nitrides can be employed to protect glass products against corrosive conditions, as coatings in solar cells.
  • the outer surface of the solar cell product is coated with only one single coating.
  • said uniform surface of the solar cell is coated with multilayered coating.
  • Several coatings can be produced in for different reasons. One reason might be to enhance the adhesion of certain coatings to glass product surfaced by manufacturing a first set of coating having better adhesion to glass surface and possessing such properties that the following coating layer has better adhesion to said layer than to glass surface itself.
  • the multilayered coating can possess several functions not achievable without said structure. The present invention accomplishes the production of several coatings in one single coating chamber or in the adjacent chambers.
  • the present invention further accomplishes the production of composite layers/coatings to solar cells ablating simultaneously one composite material target or two or more target materials comprising one or more substances.
  • a suitable thickness of an ablated layer is e.g. between 20 nm and 20 ⁇ m, preferably between 100 nm and 5 ⁇ m.
  • the coating thicknesses must not be limited to those, because the present invention accomplishes the preparation of molecular scale coatings on the other hand, very thick coatings such as 100 ⁇ m and over, on the other hand.
  • a solar cell product comprising a certain surface being coated by laser ablation wherein the coated uniform surface area comprises at least 0.2 dm 2 and that the coating has been carried by employing ultra short pulsed laser deposition wherein pulsed laser beam is scanned with a rotating optical scanner comprising at least one mirror for reflecting said laser beam.
  • said uniform surface area comprises at least 0.5 dm 2 . In a still more preferable embodiment of the invention said uniform surface area comprises at least 1.0 dm 2 .
  • the invention accomplishes easily also the products comprising uniform coated surface areas larger than 0.5 m 2 , such as 1 m 2 and over.
  • the average surface roughness of produced coating on said uniform surface area is less than 100 nm as scanned from an area of 100 ⁇ m 2 with Atomic Force Microscope (AFM).
  • AFM Atomic Force Microscope
  • the optical transmission of produced coating on said uniform surface area is no less than 88%, preferably no less than 90% and most preferably no less than 92%. In some cases the optical transparency can exceed 98%.
  • said uniform surface area is coated in a manner wherein the first 50% of said coating on said uniform surface area does not contain any particles having a diameter exceeding 1000 nm, preferably 100 nm and most preferably 30 nm.
  • said layer comprises metal, metal oxide, metal nitride, metal carbide or mixtures of these.
  • the possible metals were described earlier in description of now invented coating method.
  • said uniform surface area of glass product is coated with carbon material comprising over 90 atomic-% of carbon, with more than 70% of sp 3 -bonding.
  • carbon material comprising over 90 atomic-% of carbon, with more than 70% of sp 3 -bonding.
  • said uniform surface area comprises carbon, nitrogen and/or boron in different ratios.
  • said uniform surface area the product is coated with organic polymer material.
  • organic polymer material Such materials were described earlier in more detail in description of now invented coating method.
  • the thickness of said coating on uniform surface of glass product is between 20 nm and 20 ⁇ m, preferably between 100 nm and 5 ⁇ m.
  • the invention accomplishes also coated glass products comprising one or several atomic layer coatings and thick coatings such as exceeding 100 ⁇ m, for example 1 mm.

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FI20060177 2006-02-23
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FI20060181A FI20060181L (fi) 2006-02-23 2006-02-23 Menetelmä tuottaa pintoja ja materiaalia laserablaation avulla
FI20060178A FI20060178L (fi) 2006-02-23 2006-02-23 Pinnoitusmenetelmä
FI20060177A FI20060177L (fi) 2006-02-23 2006-02-23 Menetelmä tuottaa hyvälaatuisia pintoja ja hyvälaatuisen pinnan omaava tuote
FI20060182A FI20060182L (fi) 2005-07-13 2006-02-23 Ablaatiotekniikkaan liittyvä pinnankäsittelytekniikka ja pinnankäsittelylaitteisto
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FI20060357A FI124239B (fi) 2006-02-23 2006-04-12 Elementti, jossa on sähköä johtava kalvomainen rakenne lämmittävän ja/tai jäähdyttävän vaikutuksen synnyttämiseksi sähkövirran avulla
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US12/280,657 Expired - Fee Related US8741749B2 (en) 2006-02-23 2007-02-23 Semiconductor and an arrangement and a method for producing a semiconductor
US12/280,622 Abandoned US20090061210A1 (en) 2006-02-23 2007-02-23 Coating on a fiber substrate and a coated fiber product
US12/280,650 Abandoned US20090017318A1 (en) 2006-02-23 2007-02-23 Coating on a metal substrate and a coated metal product
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US12/280,650 Abandoned US20090017318A1 (en) 2006-02-23 2007-02-23 Coating on a metal substrate and a coated metal product
US12/280,636 Abandoned US20090136739A1 (en) 2006-02-23 2007-02-23 Coating on a plastic substrate and a coated plastic product

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