Multilayer second-order nonlinear optical films of head-to-head, mainchain chromophoric polymers

• US 5,520,968 A
• Filed: 05/05/1995
• Issued: 05/28/1996
• Est. Priority Date: 05/05/1995
• Status: Expired due to Fees

• Current Assignee: Navy The United Stated of America As Represented By The Secretary of The
• Original Assignee: the united states of america as represented by the secretary of the navy
• Inventors: Henry, deceased, Ronald A., Hoover, James M., Stenger-Smith, John, Chafin, Andrew P., Lindsay, Geoffrey A., Wynne, Kenneth J.
• Primary Examiner(s): Nagumo, Mark
• Application Number:
  US08/435,913
• Time in Patent Office: 389 Days
• Field of Search: 359/326, 359/328, 428/1, 428/333, 427/434.3
• US Class Current: 428/1.31
• CPC Class Codes: C09K 2323/031 Polarizer or dye
• CPC Class Codes: G02F 1/3616 having the non-linear optical group in the main chain
• CPC Class Codes: Y10T 428/261 In terms of molecular thickness or light wave length

Abstract

Second-order nonlinear optical polymeric films, including alternating monlecular layers of two head-to-head, mainchain, amphophilic, chromophoric polymers, one polymer having the electron donating end of the chromophore attached to hydrophilic groups, and the other polymer having the electron donating end of the chromophore attached to hydrophobic groups, and methods of fabricating the films for use in optonics.

Claims

1. A multilayer polarized film, which comprises at least one bilayer of two monomolecular layers of water-insoluble, head-to-head, mainchain, amphophilic, chromophoric polymers, one monomolecular layer A being formed of a polymer A and the other monomolecular layer B being formed of a polymer B, polymers A and B independently having two or more sequences of bridged chromophore units having the formulas ##STR8## wherein:

C and C'"'"' are chromophores of polymers A and B, respectively, wherein each chromophore has an electron accepting end represented by an arrow head, an electron donating end represented by an arrow tail, and a rigid connecting group which contains delocalized H-electrons and which is connected between the electron accepting end and the electron donating end of the chromophore;

B_L^A is a hydrophobic (lipophilic) bridging group extending between and attached to the electron accepting ends of two C'"'"' chromophores;

B_L^D is a hydrophobic (lipophilic) bridging group, extending between and attached to the electron donating ends of two C chromophores;

B_H^A is a hydrophilic bridging group extending between and attached to the electron accepting ends of two C chromophores;

B_H^D is a hydrophilic bridging group, extending between and attached to the electron donating ends of two C'"'"' chromophores;

y1 and y2 are degrees of polymerization of polymers A and B, respectively, which independently range from a minimum value of 2 to a maximum value greater than 300.

2. A multilayer polarized film, as described in claim 1, wherein each hydrophobic electron-accepting bridging group B_L^A is selected from one of the following units:

##STR9## wherein;

* designates bonds of attachment between the bridging group and a chromophore;

x₁ is an integer from 3 through 22;

x₂ is an integer from 3 through 22;

R₁ and R₂ are independently chosen from H, CH₃, and CF₃ ; and

##STR10##

3. A multilayer polarized film, as described in claim 1, wherein each hydrophobic electron-donating bridging group B_L^D is selected from one of the following units:

##STR11## wherein;

* designates bonds of attachment between the bridging group and a chromophore;

x₁ is an integer from 3 to 22; and

x₂ is an integer from 3 to 22.

4. A multilayer polarized film, as described in claim 1, wherein each hydrophilic electron-accepting bridging group B_H^A is selected from one of the following units:

##STR12## wherein;

* designates bonds of attachment between the bridging group and a chromophore;

R₁ and R₂ are independently chosen from --NO₂, --CN, and --CONH₂ ; and

R₃ is chosen from --OH, --NH₂, --CO₂ H, --CO₂ CH₃, --CONH₂, --OCH₃, --CN, and --NO₂.

5. A multilayer polarized film, as described in claim 1, wherein each hydrophilic electron-donating bridging group B_H^D is selected from one of the following units:

##STR13## wherein;

* designates bonds of attachment between the bridging group and a chromophore; and

R₃ and R₄ are one of --CH₂ OH, --CO₂ CH₃, --CONH₂, --CON(CH₃)₂, --CH₂ CO₂ CH₃, CH₂ CONH₂, CH₂ CON(CH₃)₂, --CH₂ NH₂, and --CH₂ CO₂ H.

6. A multilayer polarized film, as described in claim 1, wherein at least one of (1) the rigid connecting group of the chromophore C and (2) the rigid connecting group of the chromophore C'"'"', is selected from the following groups, in which Z is S, O, or NH:

##STR14##

7. A multilayer polarized film, as described in claim 1, which further comprises a centrosymmetric gap layer or multilayer introduced at a selected position in the multilayer polarized film.

8. A multilayer polarized film, as described in claim 7, in which the centrosymmetric gap layer or multilayer comprises a fatty acid, a fatty acid salt, or a polymer.

9. A multilayer structure, which comprises a substrate and a multilayer polarized film disposed on the substrate, wherein said multilayer polarized film comprises at least one bilayer of two monomolecular layers of water-insoluble, head-to-head, mainchain, amphophilic, chromophoric polymers which are successively deposited on the substrate by the alternating, Y-type Langmuir-Blodgett process, one monomolecular layer A being formed of a polymer A and the other monomolecular layer B being formed of a polymer B, polymers A and B independently having two or more sequences of bridged chromophore units having the formulas ##STR15## wherein:

C and C'"'"' are chromophores of polymers A and B, respectively, wherein each chromophore has an electron accepting end represented by an arrow head, an electron donating end represented by an arrow tail, and a rigid connecting group which contains delocalized n-electrons and which is connected between the electron accepting end and the electron donating end of the chromophore;

B_L^A is a hydrophobic (lipophilic) bridging group, extending between and attached to the electron accepting ends of two C'"'"' chromophores;

B_L^D is a hydrophobic (lipophilic) bridging group, extending between and attached to the electron donating ends of two C chromophores;

B_H^A is a hydrophilic bridging group, extending between and attached to the electron accepting ends of two C chromophores;

B_H^D is a hydrophilic bridging group, extending between and attached to the electron donating ends of two C'"'"' chromophores;

y1 and y2 are degrees of polymerization of polymers A and B, respectively, which independently range from a minimum value of 2 to a maximum value greater than 300.

10. A multilayer structure, as described in claim 9, in which said monomolecular layers A and B are deposited on a solid substrate by the alternating, Y-type Langmuir-Blodgett process to form at least one bilayer, wherein the sense of the polarity may be controlled by the order of deposition to yield four different multilayer structures, represented by:

space="preserve" listing-type="equation">S.sub.L (→

)(AB).sub.n

space="preserve" listing-type="equation">S.sub.L (←

)(BA).sub.n

space="preserve" listing-type="equation">S.sub.H (←

)(AB).sub.n

space="preserve" listing-type="equation">S.sub.H (→

)(BA).sub.n

wherein;

S_L is a hydrophobic (lipophilic) substrate;

S_H is a hydrophilic substrate;

AB is a bilayer in which layer A is first deposited;

BA is a bilayer in which layer B is first deposited;

n is the number of bilayers;

(→

) indicates a sense of polar order which is in a direction away from the substrate; and

(←

) indicates that a sense of polar order which is in a direction toward the substrate.

11. A multilayer structure, as described in claim 9, wherein the sense of the polarity may be changed (i.e., an inversion of dipole direction) at any desired depth in the film by depositing two monomolecular layers of the same polymer A or B at the desired depth to thus reverse the order of deposition.

12. A multilayer structure, as described in claim 11, in which the sense of the polarity is changed once to yield one of the following structures:

space="preserve" listing-type="equation">S.sub.L (→

)(AB).sub.n1 (←

)(BA).sub.n2

space="preserve" listing-type="equation">S.sub.L (←

)(BA).sub.n1 (→

)(AB).sub.n2

space="preserve" listing-type="equation">S.sub.H (←

)(AB).sub.n1 (→

)(BA).sub.n2

space="preserve" listing-type="equation">S.sub.H (→

)(BA).sub.n1 (←

)(AB).sub.n2

wherein;

S_L is a hydrophobic (lipophilic) substrate;

S_H is a hydrophilic substrate;

AB is a bilayer in which layer A is first deposited;

BA is a bilayer in which layer B is first deposited;

n1 is the number of bilayers in the first group of bilayers to be deposited;

n2 is the number of bilayers in the second group of bilayers to be deposited;

(→

) indicates a sense of polar order which is in a direction away from the substrate; and

(←

) indicates that a sense of polar order which is in a direction toward the substrate.

13. A multilayer structure, as described in claim 11, in which the sense of the polarity is changed twice to yield one of the following structures:

space="preserve" listing-type="equation">S.sub.L (→

)(AB).sub.n1 (←

)(BA).sub.n2 (→

)(AB).sub.n3

space="preserve" listing-type="equation">S.sub.L (←

)(BA).sub.n1 (→

)(AB).sub.n2 (←

)(BA).sub.n3

space="preserve" listing-type="equation">S.sub.H (←

)(AB).sub.n1 (→

)(BA).sub.n2 (←

)(AB).sub.n3

space="preserve" listing-type="equation">S.sub.H (→

)(BA).sub.n1 (←

)(AB).sub.n2 (→

)(BA)n.sub.3

wherein;

S_L is a hydrophobic (lipophilic) substrate

S_H is a hydrophilic substrate

AB is a bilayer in which layer A is first deposited;

BA is a bilayer in which layer B is first deposited;

n1 is the number of bilayers in the first group of bilayers to be deposited;

n2 is the number of bilayers in the second group of bilayers to be deposited;

n3 is the number of bilayers in the third group of bilayers to be deposited;

(→

) indicates a sense of polar order which is in a direction away from the substrate; and

(←

) indicates that a sense of polar order which is in a direction toward the substrate.

14. A multilayer polarized film, which comprises at least one bilayer of two monomolecular layers of water-insoluble, head-to-head, mainchain, amphophilic, chromophoric polymers, one monomolecular layer A being formed of a polymer A and the other monomolecular layer B being formed of a polymer B, polymers A and B independently having two or more sequences of bridged chromophore units having the formulas ##STR16## wherein:

C and C'"'"' are chromophores of polymers A and B, respectively, wherein each chromophore has an electron accepting end represented by an arrow head, an electron donating end represented by an arrow tail, and a rigid connecting group which contains delocalized n-electrons and which is connected between the electron accepting end and the electron donating end of the chromophore;

B_L^A is a hydrophobic (lipophilic) bridging group extending between and attached to the electron accepting ends of two C'"'"' chromophores;

B_L^D is a hydrophobic (lipophilic) bridging group, extending between and attached to the electron donating ends of two C chromophores;

B_H¹ is a hydrophilic bridging group, extending between and attached to the electron accepting ends of two C chromophores;

B_H^D is a hydrophilic bridging group, extending between and attached to the electron donating ends of two C'"'"' chromophores;

y1 and y2 are degrees of polymerization of polymers A and B, respectively, which independently range from a minimum value of 2 to a maximum value greater than 300;

said multilayer polarized film having a noncentrosymmetric conformation attained through successive self-assembly of polymers A and B on a surface, said noncentrosymmetric conformation being evidenced by a second-order nonlinear optical property, a piezoelectric property or a pyroelectric property.

15. A multilayer polarized film, as described in claim 14, in which polymers A and B are successively deposited on a solid substrate by the alternating, Y-type Langmuir-Blodgett process.