GB2196271A - Optical coatings - Google Patents

Optical coatings Download PDF

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Publication number
GB2196271A
GB2196271A GB08721367A GB8721367A GB2196271A GB 2196271 A GB2196271 A GB 2196271A GB 08721367 A GB08721367 A GB 08721367A GB 8721367 A GB8721367 A GB 8721367A GB 2196271 A GB2196271 A GB 2196271A
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United Kingdom
Prior art keywords
transparent
layers
refractive index
semi
layer
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.)
Granted
Application number
GB08721367A
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GB2196271B (en
GB8721367D0 (en
Inventor
Ian Robert Peterson
Peter Vincent Kolinsky
Roger Michael Wood
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.)
General Electric Co PLC
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General Electric Co PLC
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.)
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Publication date
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Publication of GB8721367D0 publication Critical patent/GB8721367D0/en
Publication of GB2196271A publication Critical patent/GB2196271A/en
Application granted granted Critical
Publication of GB2196271B publication Critical patent/GB2196271B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/18Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/20Processes for applying liquids or other fluent materials performed by dipping substances to be applied floating on a fluid
    • B05D1/202Langmuir Blodgett films (LB films)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • G02B1/105
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/56Three layers or more

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Optics & Photonics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

A method of providing a damage-resistant optical coating on a component (10) comprises depositing on the component one or more transparent or semi-transparent layers (5 - 9) of predetermined thickness by forming a required number of monomolecular layers of a material of a predetermined refractive index, using the Langmuir-Blodgett process. By use of this process, the resulting transparent or semi-transparent layers are damage-resistant, particularly to large laser output pulses. Furthermore, the thickness of the layers can be very accurately controlled, and, by adjustment of the constituents of the material in the Langmuir-Blodgett trough, the refractive index of each layer can be accurately determined. The transparent or semi-transparent layers may be alternately of high and low refractive index, and the optical thickness can be controlled to provide an anti-reflective or reflective coating.

Description

SPECIFICATION Optical coatings This invention relates to optical coatings, and particularly to damage-resistant optical coatings and components provided with such coatings.
With the use of high power lasers there is a requirement that optical coatings, for example anti-reflection coatings, carried by optical components shall be damage resistant. Such coatings may be damaged at optical flux density thresholds which are much less than those of bulk components.
Conventional methods of fabrication of such coatings involve thermal or electron beam evaporation. The laser induced damage thresholds of these coatings are limited by hollow pores, defects and substrate replication defects and are typically of the order of 1 to 5 Jcm-2 for Q-switched pulse irradiation. At present, the most favoured technique for the production of damage-resistant optical coatings is the sol-gel process. In such a process a liquid alkoxy compound of a high refractory metal oxide is hydrolysed to form a hydrated gel, which is then fired to give a uniform glassy layer of the metal oxide. Coatings produced by such a process exhibit damage thresholds typically of the order of 10 Jcm-2. This threshold is, however, limited by the number of small hollow pores produced during the deposition process.
Recently, damage-resistant optical coatings have been produced by molecular beam epitaxy. Unfortunately, however, this technique is extremely slow, and employs very sophisticated and expensive equipment.
It is an object of the present invention to provide an improved method forming a damage-resistant optical coating on a component.
According to the invention, a method of providing a damage-resistant optical coating on a component comprises depositing on the component at least one transparent or semitransparent layer of predetermined thickness by forming a required number of monomolecular layers of a material of predetermined refractive index using the Langmuir-Blodgett process.
If the component comprises a substrate of a material of refractive index nS and a single transparent or semi-transparent layer is formed thereon, the refractive index of that layer is preferably q and the thickness is preferably A/4, whereby an antireflective coating is formed.
The coating may comprise a plurality of said transparent or semi-transparent layers, each formed from a material having a refractive index which is different from that of the material forming the or each layer adjacent thereto.
For an antireflective coating, the method then preferably comprises depositing a relatively small number (e.g. 2-5) of alternate layers of respectively high and low refractive indices. Preferably the thickness of each layer multiplied by its refractive index is approximately 0.72/4, where A is the wavelength of the incident light.
Alternatively, the optical coating may be a reflective coating, in which case the method comprises depositing a relatively large odd number (e.g. 11-81) of alternate layers of respectively high and low refractive indices and of substantially A/4 thickness.
Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings, in which: Figures 1 and 2 show schematic cross sections of damage-resistant optical coatings in accordance with the invention, which coatings are respectively anti-reflective and reflective; and Figure 3 shows a schematic cross section of an alternative coating.
The coatings are produced by using the Langmuir-Blodgett technique to deposit a chosen number of monomolecular layers (monolayers) on a surface of an optical component, by which technique the thickness of the coating may be defined with great accuracy, and will be uniform over the whole surface. Defects within the coating may be removed while each monolayer is on the surface of the water within the Langmuir-Blodgett trough prior to deposition on the component. One way of achieving this is to apply pressure to the monolayer trapped at the air-water interface in the manner described in Sci. Prog.
Oxf. volume 69, 1985, pages 533-550.
Referring to Figure 1, a damage-resistant anti-reflective coating 1 is formed on a glass substrate 2 of refractive index 1.5. The coating comprises a first layer 3 which has a refractive index of 2.5 in the visible band, formed by depositing successive monolayers of hemicyamine, using the Langmuir-Blodgett (LB) process. The thickness d of the layer 3 is preferably such that d x 2.5 = 0.71/4. For example, if A is 1000nm, then 2.5d = 175nm and d = 70nm.
Assuming that a single LB layer has a thickness of 1.5nm, the number of LB layers required will be 70/1.5 47. A monomolecular layer of the material is deposited on the surface of the liquid in the Langmuir-Blodgett trough and the substrate is passed through the layers forty-seven times to achieve the required thickness, ensuring, throughout, that a monomolecular layer of the material is maintained on the surface. Since each LB layer is a single molecule thick, the thickness of the layer 3 can be controlled to within 1.5nm.
A second layer 4 of refractive index 1.5 is then deposited over the layer 3 by the LB process. This layer can be formed of 22 tricosenoic acid and would be of 175/1.5nm = 117nm thickness. If a single monomolecular layer of the material has a thickness of 3nm, the number of such layers required will be 117/3 = 39.
The refractive indices of the layers can be controlled accurately during deposition by slight adjustment of the constituents of the materials in the LB trough, for example by the incorporation of additives therein.
Figure 2 shows schematically a section through a reflective coating. In this case, layers 5, 6 and 7 of refractive index 2.5 interleaved with layers 8 and 9 of refractive index 1.5 are deposited on a substrate 10 of refractive index 1.5. The layers are deposited by the LB process as described above, but each will be of /4 optical thickness. The number of passes through the monomolecular layer in the LB trough will be determined accordingly, as in the previous embodiment.
Any desired number of layers of alternately high and low refractive indices may be deposited, depending upon the required reflective or antireflective characteristics of the coating.
An alternative method of controlling the refractive index of a layer is provided by skeletonisation. This involves the deposition of a mixture of the required coating material with a soluble material. After deposition of the layer, the soluble material is at least partially removed, leaving a skeleton of the coating material. The refractive index is reduced by an amount depending upon the degree of skeletonisation. The limit is reached when the layer only just remains continuous. One material which an be used in this way is cadmium eicosanoate, which would normally have a refractive index of 1.526. By use of skeletonisation, a refractive index of, say, 1.23 may be obtained. Such materials as 22-tricosenoic acid may be partially polymerised after skeletonisation.If the skeletonised layer is formed on a layer of unskeletonised cadmium eicosanoate, a good antireflective coating will be formed, since 1.232 =: 1.526. Similarly, skeletonised cadmium eicosanoate on glass of refractive index 1.5 will produce a good antireflective coating.
Figure 3 shows an example of a structure in which the thickness of successive high refractive index layers 11, 13, 15, 17, 19 decreases, and the thickness of successive low refractive index layers 12, 14, 16, 18 increases, with distance from the substrate. For the sake of explanation, the layers are shown divided by dotted lines which are spaced apart by a notional unit thickness. In the figure, the high refractive index layers 11, 13, 15, 17 and 1 9 are respectively 5, 4, 3, 2 and 1 units thick, and the low refractive index layers 12, 14, 16 and 18 are respectively 1, 2, 3 and 4 units thick. This arrangement gives a graded optical characteristic, which is particularly advantageous for handling high power flux densities e.g. for laser output windows where the laser pulse passes through the coating.The graded index gives minimal electrical field discontinuities.
The refractive index of any indvidual layer of a coating may be graded through the thickness of the layer by slight changes in the composition of the material in the LB trough during the course of the passes of the substrate through the material.
Examples of other materials which may be deposited by the LB process are eicosanoates of other heavy metals besides cadmium, eicosenoic acid, which has a refractive index of 1.425 at a wavelength of 632 nm, and 22gedye, which has a refractive index of 4.2 at that wavelength.
Measurements have shown that optical coatings comprising monolayers of hemacyamine deposited by the LB process may withstand fluxes in excess of 100J/cm2 for 25ns pulses of a 1.0464 ijm wavelength laser.
It will be apparent that the present invention provides a simple method of providing damage-resistant coatings on optical components, by which method the thickness and the refractive indices of the various layers can be very accurately controlled.

Claims (13)

1. A method of providing a damage-resistant optical coating on a component, comprising depositing on the component at least one transparent or semi-transparent layer of predetermined thickness by forming a required number of monomolecular layers of a material of predetermined refractive index using the Langmuir-Blodgett process.
2. A method as claimed in Claim 1, comprising depositing a plurality of said transparent or semi-transparent layers, each formed from a material having a refractive index which is different from that of the material forming the or each layer adjacent thereto.
3. A method as claimed in Claim 2, wherein the transparent or semi-transparent layers are alternately of materials of high and low refractive index values.
4. A method as claimed in Claim 2 or Claim 3, wherein the number of monomolecular layers deposited by the Langmuir-Blodgett process is such that the thickness d of each transparent layer or semi-transparent layer is given by d = 0.7 44n where n is the refractive index of the particular layer and is the wavelength of the incident light.
5. A method as claimed in Claim 2 or Claim 3, wherein the number of monomolecular layers deposited by the Langmuir-Blodgett process is such that the thickness of each transparent or semi-transparent layer is substantially equal to zl/4, where A is the wavelength of the incident light.
6. A method as claimed in Claim 2 or Claim 3, wherein the number of monomolecular layers deposited by the Langmuir-Blodgett process is such that the thickness of the transparent or semi-transparent layers of high refractive index value decreases with distance from the substrate and the thickness of the layers of low refractive index increases with distance from the substrate.
7. A method as claimed in any preceding claim, wherein the material of at least one of the of the transparent or semi-transparent layers comprises a fatty acid.
8. A method as claimed in Claim 7, wherein the fatty acid is 22-tricosenoic acid or the eicosanoate of a heavy metal such as cadmium.
9. A method as claimed in any one of Claim 1-6, wherein the material of at least one of the transparent layers or semi-transparent layers is hemicyanine.
10. A method as claimed in any preceding claim, wherein the refractive index of at least one of the tansparent or semi-transparent layers is reduced by skeletonisation of the material of the layer.
11. A method as claimed in Claim 10, wherein the material is at least partially polymerised after skeletonisation thereof.
12. A method of providing a damage-resistant optical coating on a component, substantially as hereinbefore described with reference to the accompanying drawing.
13. A component provided with a coating by a method as claimed in any preceding claim.
GB8721367A 1986-09-15 1987-09-11 Optical coatings Expired - Fee Related GB2196271B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB868622158A GB8622158D0 (en) 1986-09-15 1986-09-15 Optical coatings

Publications (3)

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GB8721367D0 GB8721367D0 (en) 1987-10-21
GB2196271A true GB2196271A (en) 1988-04-27
GB2196271B GB2196271B (en) 1990-01-10

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GB868622158A Pending GB8622158D0 (en) 1986-09-15 1986-09-15 Optical coatings
GB8721367A Expired - Fee Related GB2196271B (en) 1986-09-15 1987-09-11 Optical coatings

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WO (1) WO1988001909A1 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2168622A (en) * 1984-12-21 1986-06-25 Gen Electric Plc Stabilised Langmuir-Blodgett films

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1916092A1 (en) * 1969-03-27 1970-10-08 Minnesota Mining & Mfg Transparent optical element coated with a polymer of a
JPS5390316A (en) * 1977-01-20 1978-08-09 Nippon Chemical Ind Reflectionnproof film
FR2541936B1 (en) * 1983-03-04 1985-10-04 Commissariat Energie Atomique METHOD AND DEVICE FOR PRODUCING ALTERNATE MONOMOLECULAR LAYERS
DE3369568D1 (en) * 1983-03-11 1987-03-05 Toray Industries Transparent material having antireflective coating
DE3584779D1 (en) * 1984-02-13 1992-01-16 Univ Marquette ASSEMBLING SEVERAL LAYERS OF A POLYMERIZABLE SURFACE ACTIVE SUBSTANCE ON THE SURFACE OF A SOLID MATERIAL.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2168622A (en) * 1984-12-21 1986-06-25 Gen Electric Plc Stabilised Langmuir-Blodgett films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PHYSICS IN TECHNOLOGY, VOL 12, (1981), G.G. ROBERTS ET AL }TECHNOLOGICAL APPLICATIONS OF LANGMUIR-BLODGETT FILMS, SEE PAGE 71 LINES 53-54 *

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Publication number Publication date
GB8622158D0 (en) 1987-02-04
GB2196271B (en) 1990-01-10
GB8721367D0 (en) 1987-10-21
WO1988001909A1 (en) 1988-03-24

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19920911