EP1032943A2 - Procede de production d'un plasma par exposition a des micro-ondes - Google Patents

Procede de production d'un plasma par exposition a des micro-ondes

Info

Publication number
EP1032943A2
EP1032943A2 EP98955327A EP98955327A EP1032943A2 EP 1032943 A2 EP1032943 A2 EP 1032943A2 EP 98955327 A EP98955327 A EP 98955327A EP 98955327 A EP98955327 A EP 98955327A EP 1032943 A2 EP1032943 A2 EP 1032943A2
Authority
EP
European Patent Office
Prior art keywords
plasma
pulsed
microwave
microwave radiation
radiation
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
EP98955327A
Other languages
German (de)
English (en)
Inventor
Thomas Weber
Johannes Voigt
Susanne Lucas
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
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 Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP1032943A2 publication Critical patent/EP1032943A2/fr
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H01J37/32266—Means for controlling power transmitted to the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32697—Electrostatic control
    • H01J37/32706—Polarising the substrate

Definitions

  • the invention relates to a method for generating a plasma by irradiation of microwaves, a process gas being passed into a recipient, microwave radiation being generated by means of a radiation source and this microwave radiation being irradiated into the recipient so that a plasma is ignited.
  • Processes in which microwave radiation is generated and a plasma is thus ignited are known and are used in a wide variety of areas. These can be independent processes or part of a sequence of different processes.
  • the plasma generated by the microwave radiation can also be used to ignite another plasma.
  • An important area of application is the treatment of surfaces. These include both coating and non-coating, e.g. B. understood removal or activating method.
  • the coating processes the coating of plastics and hardened steels with a hard wear protection layer is of particular importance. With such a wear protection layer, it can, for. B. act a hard, amorphous carbon layer (aC: H).
  • DE 195 13 614 describes the deposition of carbon layers with applied bipolar pulsed Bias.
  • US 5,427,827 is concerned with the deposition of optically transparent, diamond-like carbon layers in continuous microwave ECR plasma at a substrate temperature of 50 ° C., a sinusoidal RF alternating voltage is applied.
  • the so-called downstream method is described, in which the plasma generation and the layer deposition take place spatially separated in two chambers.
  • No. 4,869,923 relates to a method in which a plasma is generated by continuous irradiation of microwaves, but without a bipolar pulsed bias.
  • a disadvantage of these known processes is that the typical process temperatures are around 180-220 ° C. for the deposition of hard layers a few ⁇ m thick at high deposition rates. These high temperatures can cause the substrate to lose hardness.
  • a coating of art Material substrates are not easily possible with this method, since the plastic softens due to the temperature load, so that the substrates change their shape.
  • One can remedy this by reducing the incident microwave power. This also reduces the coating rate, so that the process time is extended again.
  • Another remedy is to insert pause times between the bipolar substrate pulses to accelerate the ions.
  • both the generation of the plasma and the acceleration of the ions onto the substrates are brought about together by a high-frequency, sinusoidal AC voltage on the substrates.
  • the process temperature here is around 150 ° C.
  • a disadvantage of this method is that, for technical reasons, scaling to large batches such as. B. the industrially customary batch sizes are not readily possible.
  • the method according to the invention in which a pulsed microwave radiation is used to generate the plasma, has the advantage that the process temperature can be set to less than 200 ° C. and scaling to large batch quantities is possible.
  • the method according to the invention is therefore particularly suitable for treatment of temperature-sensitive substrates and for the treatment of batch sizes customary in industry.
  • the lowering of the process temperature is made possible by the fact that the coupled power of the pulsed microwave radiation can be reduced with the same process result in comparison to the required power of the non-pulsed microwave radiation.
  • the method according to the invention is based on the knowledge that the ion current density, which can be extracted from a plasma generated by microwave rays and can act on the substrates, increases disproportionately to the coupled power of the microwave radiation. If you double the power of the coupled microwave radiation, the ion current also increases, but by more than twice. In the prior art, the power of the continuous microwave radiation is therefore reduced until the desired ion current density is reached. In the method according to the invention, instead, a high power of the microwave radiation is assumed and the plasma is ignited by a pulsed excitation.
  • the reduction in the effective power of the microwave radiation with the same process result leads to a lowering of the process temperature.
  • the method according to the invention is therefore particularly well suited for the treatment of temperature-sensitive substrates.
  • the process rate is increased when the microwave radiation power is effectively the same. This reduces the process time.
  • the process is therefore faster and cheaper and is therefore scalable to large batch quantities.
  • the method according to the invention can naturally be used in all microwave-assisted processes. This can be an independent process. But it can also be part of a sequence of different processes.
  • the processes can be those for surface treatment, which can be coating or non-coating.
  • a distinction is made between abrasive and non-abrasive processes, e.g. B. activating processes.
  • the microwave radiation can be combined with other sources for particles, electromagnetic radiation or particle radiation, for example sputter sources, evaporator sources or arc sources.
  • the microwave plasma itself can be used in various ways depending on the process in which it is used, for example as a plasma source or as an ion source. These ions can be accelerated onto the substrates by means of a negative substrate voltage.
  • the microwave plasma can also be used as an ignition aid for other plasmas.
  • Figure 1 is a graphical representation of the dependence of the average power of the microwave radiation on the power per microwave pulse for a constant average ion current on the substrates;
  • Figure 2 is a schematic representation of an apparatus for performing the method according to the invention
  • FIG. 3 shows a section along the line III-III in FIG.
  • FIG. 1 again illustrates how the method according to the invention reduces the effective output of the microwave radiation with the same process result.
  • the effective power of the microwave radiation is calculated from the radiation power per pulse multiplied by the value for the duty cycle. This is set so that the ion current density, that is to say the bias current on the substrates, is reduced to the initial value and kept constant. It can be seen from the plot that if the pulse power is increased, the effective microwave power can be reduced with the same effect.
  • FIG. 2 and 3 schematically show a device 1 for performing the method according to the invention.
  • the device 1 has a recipient 2 which is circular in cross section and has a diameter of approximately 70 cm.
  • Substrates 3 are set in recipient 2.
  • the substrates are steel.
  • double-rotating substrates 3 are provided, which rotate in the direction of arrows A and B in FIG. 3 both about themselves and about the center of the recipient 2.
  • the substrates 3 are connected to a voltage source 4, so that a negative bias supply can be applied, which can also be pulsed.
  • the recipient 2 has an opening 5 through which a microwave radiation generated by a voltage source 6 can be coupled. Furthermore, a supply nozzle 7 for the introduction of the process gas and a suction nozzle 8 with a control valve 9 are provided for applying the required vacuum.
  • the recipient 2 also has two further radiation sources 10 and 11, in the present case two sputter cathodes.
  • the substrates were plasma cleaned in a known manner by igniting an Ar plasma with a negative voltage applied to the substrates. This serves to clean and increase the adhesion of the layer to be subsequently applied.
  • a metallic layer is applied by a known method, which increases the adhesion of the functional layer to be subsequently applied.
  • a bipolar bias voltage was applied to the substrates.
  • the time average of the substrate voltage was -200V.
  • the recipient 1 is coupled to two sputter sources 10, 11. In this way, a sputtering process can be used in addition to the coating process. Coupling with other sources of electromagnetic or particle radiation such as evaporator sources and arc sources are also conceivable.
  • the temperature of the unpulsed process was approx. 220 ° C. After pulsing, the temperature was reduced to below 200 ° C.
  • amorphous carbon layers a-C: H
  • the properties of the layers produced were:
  • the frequency of the alternating frequency can be less than, equal to or greater than the frequency of the microwave. In the case of frequency equality, it can be advantageous to set the phase between the bias pulse and the microwave pulse in a defined manner.
  • Possible alternating frequencies are a sinusoidal voltage curve over time, a pulse-like monopolar voltage and a pulse-like bipolar voltage with or without pauses between the individual voltage pulses.
  • the microwave frequency can be in the industrial frequency range, for example at 2.45 GHz, 1.225 GHz and 950 MHz GHz.
  • the efficiency of pulsing can be increased with the microwave power.
  • the above The limit of the power of the microwave radiation is equal to the power limit of the radiation source used. A lower limit of 0.5 kW is recommended. Values above 1 kW or above 3 kW are particularly preferred.
  • microwave plasmas can be used.
  • pure microwave plasmas can be used in a pressure range> 10 mbar, or with an additional magnetic field as ECR microwave plas a in a pressure range> 10 mbar.
  • the method according to the invention is suitable for all types of coating microwave plasmas.
  • C-containing layers e.g. B. methane and acetylene can be used as process gases.
  • Silanes are suitable for the production of silicon-containing layers, e.g. Silane, or organosilicon compounds such as HMDS, HMDS (0), HMDS (N) or TMS as process gases.
  • organosilicon compounds such as HMDS, HMDS (0), HMDS (N) or TMS
  • process gases known to those skilled in the art such as, for. B. organometallic compounds can be used.
  • the method is also suitable for the deposition of plasma polymer layers. It is also possible to separate layer systems by combining different gases.
  • the layer can be deposited by the method described with other layers, in particular those which are deposited by known methods.
  • the combination can take place, for example, in multiple or multiple layers.
  • the process gas can also be exchanged during the pulse pauses, so that each plasma pulse starts with fresh process gas. This can be important for the treatment and coating of substrates with complex geometrical relationships.
  • the substrates can be moved upright, rotating or linear.
  • the process can of course be carried out in other types of plants, such as batch plants or continuous plants or bulk goods plants.
  • the method according to the invention is also suitable for non-coating processes for surface activation, for the plasma fine cleaning of surfaces or for the plasma structuring of surfaces. It also advantageously allows lower treatment temperatures or a faster process, i. H. a reduction in process time.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Plasma Technology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé de production d'un plasma par exposition à des micro-ondes, selon lequel un gaz utilisé est amené dans un récipient et un plasma est allumé par exposition à des micro-ondes. Selon l'invention, le rayonnement micro-onde injecté est pulsé, ce qui permet de réduire la puissance effective des micro-ondes pour un résultat identique et, par conséquent, d'abaisser la température du processus. Cela permet également d'augmenter le rendement du processus pour une puissance injectée effective identique et, ainsi, de réduire la durée du processus et d'augmenter considérablement les quantités de charge.
EP98955327A 1997-09-17 1998-09-15 Procede de production d'un plasma par exposition a des micro-ondes Ceased EP1032943A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19740792A DE19740792A1 (de) 1997-09-17 1997-09-17 Verfahren zur Erzeugung eines Plasmas durch Einstrahlung von Mikrowellen
DE19740792 1997-09-17
PCT/DE1998/002727 WO1999014787A2 (fr) 1997-09-17 1998-09-15 Procede de production d'un plasma par exposition a des micro-ondes

Publications (1)

Publication Number Publication Date
EP1032943A2 true EP1032943A2 (fr) 2000-09-06

Family

ID=7842575

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98955327A Ceased EP1032943A2 (fr) 1997-09-17 1998-09-15 Procede de production d'un plasma par exposition a des micro-ondes

Country Status (5)

Country Link
US (1) US20030012890A1 (fr)
EP (1) EP1032943A2 (fr)
JP (1) JP2001516947A (fr)
DE (1) DE19740792A1 (fr)
WO (1) WO1999014787A2 (fr)

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US7560175B2 (en) * 1999-12-31 2009-07-14 Lg Chem, Ltd. Electroluminescent devices with low work function anode
KR100721656B1 (ko) * 2005-11-01 2007-05-23 주식회사 엘지화학 유기 전기 소자
DE10000663C2 (de) * 2000-01-11 2003-08-21 Schott Glas Verfahren zum Beschichten eines Substrats
DE10202311B4 (de) * 2002-01-23 2007-01-04 Schott Ag Vorrichtung und Verfahren zur Plasmabehandlung von dielektrischen Körpern
FR2871812B1 (fr) * 2004-06-16 2008-09-05 Ion Beam Services Sa Implanteur ionique fonctionnant en mode plasma pulse
EP1794255B1 (fr) * 2004-08-19 2016-11-16 LG Chem, Ltd. Dispositif lumineux organique comprenant une couche tampon et procede de fabrication correspondant
KR100890862B1 (ko) * 2005-11-07 2009-03-27 주식회사 엘지화학 유기 발광 소자 및 이의 제조 방법
US8680693B2 (en) * 2006-01-18 2014-03-25 Lg Chem. Ltd. OLED having stacked organic light-emitting units
EP1918967B1 (fr) 2006-11-02 2013-12-25 Dow Corning Corporation Procédé de formation d'une couche par déposition à partir d'un plasma
DE102007021386A1 (de) * 2007-05-04 2008-11-06 Christof-Herbert Diener Kurztaktniederdruckplasmaanlage
JP5120924B2 (ja) * 2007-05-25 2013-01-16 トヨタ自動車株式会社 アモルファスカーボン膜の製造方法
US20090091242A1 (en) * 2007-10-05 2009-04-09 Liang-Sheng Liao Hole-injecting layer in oleds
WO2010151337A1 (fr) * 2009-06-26 2010-12-29 Tokyo Electron Limited Amélioration de l'adhésivité d'un film d'hydrocarbure fluoré (cfx) par dopage de carbone amorphe
DE102010035593B4 (de) * 2010-08-27 2014-07-10 Hq-Dielectrics Gmbh Verfahren und Vorrichtung zum Behandeln eines Substrats mittels eines Plasmas
DE102011100057A1 (de) * 2011-04-29 2012-10-31 Centrotherm Thermal Solutions Gmbh & Co. Kg Vorrichtung und verfahren zum behandeln von substraten mit einem plasma
TWI620227B (zh) * 2011-07-27 2018-04-01 日立全球先端科技股份有限公司 電漿處理裝置及電漿蝕刻方法
JP6102816B2 (ja) * 2014-03-31 2017-03-29 ブラザー工業株式会社 成膜装置、成膜方法及び成膜プログラム
JP6107731B2 (ja) * 2014-03-31 2017-04-05 ブラザー工業株式会社 成膜装置

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Also Published As

Publication number Publication date
WO1999014787A2 (fr) 1999-03-25
US20030012890A1 (en) 2003-01-16
DE19740792A1 (de) 1999-04-01
JP2001516947A (ja) 2001-10-02
WO1999014787A3 (fr) 1999-05-06

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