Process and arrangement for photothermal spectroscopy

Claim 2

A process for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the laser beam after interaction with the object, an additional modulation of the intensity is determined as an optical response of the object by a measurement detector, comprising the steps of performing: a) intensity modulation of the laser beam before it impinges on the object, whose modulation spectrum substantially contains only a carrier frequency (f 1 ) and two sideband frequencies (f 1 ±f 2 ), the sideband frequencies (f 1 ±f 2 ) resulting as an amplitude modulation of a base frequency (f 2 ), b) eliminating a component of the base frequency (f 2 ) having the same phase as a mixed frequency resulting from the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) by means of feeding back said detected component as an interference variable to the modulation step, and c) measuring the amplitude of that component of the base frequency (f 2 ) which is contained in the beam leaving the object as a photothermal modulation product in phase with the mixed frequency of the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) by the use of a frequency-selective and phase-selective device.

Claim 3

The process according to claim 1, wherein the phase relation of frequency f 1 and its sidebands f 1 ±f 2 is periodically reversed by 180° at a frequency which is less than frequency f 2 .

Claim 4

The process according to claim 1, wherein the component of frequency f 2 which is contained in the modulation spectrum of the intensity of the laser beam directed on the object and in quadrature with the mixed frequency of the carrier frequency and sideband frequencies is also detected by means of another frequency-selective and phase-selective device and is supplied as an interference signal to another control loop influencing the modulation spectrum for the purpose of adjusting the detected component to the value of zero.

Claim 5

The process according to claim 1, wherein the laser beam is generated by an intensity-modulated laser diode.

Claim 6

The process according to claim 1, wherein the laser beam passes one or more optical modulators in the beam path between the laser source and the object.

Claim 7

The process according to claim 1, wherein the intensity modulation is effected in that the laser beam is composed of two partial beams susceptible to interference, the mean values of the optical frequencies of the two partial beams differing by the value of frequency f 1 , and the optical frequency of one partial beam is frequency-modulated with a signal of the base frequency f 2 .

Claim 8

The process according to claim 1, wherein the intensity modulation is effected in that the laser beam is composed of two partial beams susceptible to interference, the mean values of the optical frequencies of the two partial beams differing by the value of frequency f 1 , and the optical phase position of one partial beam is phase-modulated with a signal of base frequency f 2 .

Claim 9

The process according to claim 1, wherein the intensity modulation of the laser beam is effected in such a way that a modulation period of duration T=1/f 2 comprises a time segment of duration T 1 , in which the intensity is modulated with a periodic signal of carrier frequency f 1 , and a time segment of duration T 2 , in which the intensity is constant, and its value is adjusted by said control loop so that the component of the frequency spectrum in phase with frequency f 2 has an intensity of zero.

Claim 10

The process according to claim 8, wherein an integral number of periods of duration 1/f 1 is contained within the time segment T 1 .

Claim 11

The process according to claim 9, wherein the modulation with frequency f 1 within time segment T 1 is effected in such a way that the start of this time segment does not coincide with a zero axis crossing of the oscillation of frequency f 1 .

Claim 12

The process according to claim 3, wherein the influencing of the modulation spectrum by changing the time period is effected between the start of time segment T 1 and the zero axis crossing of the oscillation of frequency f 1 .

Claim 13

The process according to claim 8, wherein the time segments T 1 and T 2 are of equal duration.

Claim 14

The process according to claim 8, wherein the influencing of the modulation spectrum by changing the intensity is effected within time segment T 2 .

Claim 15

The process according to claim 8, wherein a square-wave modulation is effected within the time segment T 1 .

Claim 16

The process according to claim 14, wherein the modulation spectrum is influenced by changing the pulse-duty factor.

Claim 17

The process according to claim 14, wherein the modulation spectrum is influenced by changing the rise time and fall time of the square-wave pulses.

Claim 18

The process according to claim 6, wherein a modulation form is produced in that the laser beam is composed of two partial beams susceptible to interference, the optical frequency of one partial beam being modulated with a signal of period T in such a way that it differs from the optical frequency of the other partial beam in time segment T 1 by the value of frequency f 1 .

Claim 19

The process according to claim 7, wherein a modulation form is produced in that the laser beam is composed of two partial beams susceptible to interference, the optical phase position of one partial beam being modulated with a signal of period T in such a way that the phase difference changes periodically relative to the other partial beam in time segment T 1 with the base frequency f 1 and remains constant in time portion T 2 .

Claim 20

The process according to claim 1, wherein a proportion of the light directed on the object is decoupled to a reference detector for generating a reference value and the differential signal is evaluated by the measurement detector and reference detector.

Claim 21

The process according to claim 19, wherein a regulating detector is also used simultaneously as a reference detector.

Claim 22

In an arrangement for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the laser beam after interaction with the object, an additional modulation of the intensity is determined as an optical response of the object by a measurement detector, the improvement comprising: a) means for performing intensity modulation of the laser beam before it impinges on the object, whose modulation spectrum substantially contains only a carrier frequency (f 1 ) and two sideband frequencies (f 1 ±f 2 ), the sideband frequencies (f 1 ±f 2 ) resulting as an amplitude modulation of a base frequency (f 2 ); b) means for eliminating a component of the base frequency (f 2 ) having the same phase as a mixed frequency resulting from the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) by means of feeding back said detected component as an interference variable to the modulation means; and c) means for measuring the amplitude of that component of the base frequency (f 2 ) which is contained in the beam leaving the object as a photothermal modulation product by the use of a frequency-selective device.

Claim 23

In an arrangement for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the laser beam after interaction with the object, an additional modulation of the intensity is determined as an optical response of the object by a measurement detector, the improvement comprising: a) means for performing intensity modulation of the laser beam before it impinges on the object, whose modulation spectrum substantially contains only a carrier frequency (f 1 ) and two sideband frequencies (f 1 ±f 2 ), the sideband frequencies (f 1 ±f 2 ) resulting as an amplitude modulation of a base frequency (f 2 ); b) means for eliminating a component of the base frequency (f 2 ) having the same phase as a mixed frequency resulting from the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) by means of feeding back said detected component as an interference variable to the modulation means; and c) means for measuring the amplitude of that component of the base frequency (f 2 ) which is contained in the beam leaving the object as a photothermal modulation product by the use of a frequency-selective device.

Claim 24

The arrangement of claim 21, wherein said amplitude measuring means measures the photothermal modulation product in phase with the mixed frequency of the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) wherein the device is also phase selective.

Claim 25

The arrangement of claim 21, wherein said means for eliminating a component of the base frequency includes a semireflecting mirror arranged after the modulation means for decoupling a partial beam of the modulated laser beam to a regulating detector, said regulating detector being connected with an electronic modulator group at an output side via a lock-in amplifier acting as a frequency-selective and phase-selective device, said modulator group being coupled to a control input of said modulator means.

Claim 26

The arrangement of claim 22, wherein said means for measuring includes a lock-in detector acting as a frequency-selective and phase-selective device and being arranged in the beam path after interaction of the laser beam with the object, said lock-in detector is adapted to be timed to the base frequency.

Claim 27

The arrangement of claim 21, wherein said laser source and modulator means are combined in an intensity-modulated laser diode.

Claim 28

In an arrangement for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the incident laser beam, the object impresses an additional modulation of intensity on the laser beam in the path of the beam after interaction with the object, a measurement detector being arranged for detecting this additional modulation as an optical response of the object, the improvement comprising: a laser source and a modulator which are provided for generating the intensity-modulated laser beam, said modulator having a modulation spectrum substantially containing only three frequencies in the form of the carrier frequency (f 1 ) with the first sidebands (f 1 ±f 2 ), which three frequencies result from a carrier frequency (f 1 ) and a base frequency (f 2 ); a semireflecting mirror which is arranged after the modulator for decoupling a partial beam of the modulated laser beam to a regulating detector, said regulating detector being connected with an electronic modulator group at the output side via a lock-in amplifier acting as a frequency-selective and phase-selective device, said modulator group being coupled to the control input of the modulator for supplying an appropriate interference signal of the base frequency (f 2 ) so as to compensate for an unwanted component of the base frequency (f 2 ) produced from the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) by modulation nonlinearities; and a measurement detector having an output which is connected with a lock-in detector acting as a frequency-selective and phase-selective device, said measurement detector being arranged in the beam path after interaction of the laser beam with the object, said lock-in detector of the modulator group being adapted or tuned to the base frequency (f 2 ) which is generated as a result of photothermal modulation of the index of refraction by mixing the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) in the object.

Claim 29

In an arrangement for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the incident laser beam, the object impresses an additional modulation of intensity on the laser beam in the path of the beam after interaction with the object, a measurement detector being arranged for detecting this additional modulation as an optical response of the object, the improvement comprising: a laser source and a modulator which are provided for generating the intensity-modulated laser beam, said modulator having a modulation spectrum substantially containing only three frequencies in the form of the carrier frequency (f 1 ) with the first sidebands (f 1 ±f 2 ), which three frequencies result from a carrier frequency (f 1 ) and a base frequency (f 2 ); a semireflecting mirror which is arranged after the modulator for decoupling a partial beam of the modulated laser beam to a regulating detector, said regulating detector being connected with an electronic modulator group at the output side via a lock-in amplifier acting as a frequency-selective and phase-selective device, said modulator group being coupled to the control input of the modulator for supplying an appropriate interference signal of the base frequency (f 2 ) so as to compensate for an unwanted component of the base frequency (f 2 ) produced from the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) by modulation nonlinearities; and a measurement detector having an output which is connected with a lock-in detector acting as a frequency-selective and phase-selective device, said measurement detector being arranged in the beam path after interaction of the laser beam with the object, said lock-in detector of the modulator group being adapted or tuned to the base frequency (f 2 ) which is generated as a result of photothermal modulation of the index of refraction by mixing the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) in the object.

Claim 30

The arrangement according to claim 26, wherein said laser source and modulator are combined in an intensity-modulated laser diode which is controlled by the modulator.

Claim 31

The arrangement according to claim 25, wherein another modulator is arranged directly downstream of said modulator and is controlled by a modulation signal of the base frequency (f 2 ) which is variable with respect to amplitude, wherein another modulator group is provided for controlling, which modulator group is connected on the input side with the base (f 2 ) supplied by the modulator group and which has control input, the lock-in amplifier providing a corresponding regulating variable via said control input for regulating the amplitude.

Claim 32

In an arrangement for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the incident laser beam, the object impresses an additional modulation of intensity on the laser beam in the path of the beam after interaction with the object, a measurement detector is arranged for detecting this additional modulation as an optical response of the object, the improvement comprising: a laser source and an optical phase shifter and optical frequency modulator, which are provided for generating the intensity modulated beam, said elements providing means for effecting the intensity modulation of the laser beam in such a way that a modulation period of duration T=1/f 2 , where f 2 is a base frequency, comprises a time segment duration T 1 , in which the intensity is modulated with a periodic signal of carrier frequency f 1 , and a time segment duration T 2 , in which the intensity is constant; a semireflecting mirror being arranged in the intensity-modulated laser beam prior to interaction with the object for decoupling a beam to a regulating detector, and the regulating detector being connected with the electronic modulator group at the output side via a lock-in amplifier acting as a frequency-selective and phase-selective device, wherein the modulator group supplies a control signal to the phase shifter such that the phase displacement results in an intensity value for the elimination of an interfering component of the base frequency (f 2 ); and a measurement detector having an output which is coupled to a lock-in detector acting as a frequency-selective and phase-selective device, said detector beam being arranged in the beam path after interaction of the laser beam with the object, wherein the lock-in detector of the modulator group is adapted or tuned to the base frequency (f 2 ) which is generated as a result of photothermal modulation of the index of refraction by mixing the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) in the object.

Claim 33

In an arrangement for photothermal spectroscopy in which an intensity-modulated laser beam is directed on an object to be examined and in which, as a result of a reaction of the object to energy applied by the incident laser beam, the object impresses an additional modulation of intensity on the laser beam in the path of the beam after interaction with the object, a measurement detector is arranged for detecting this additional modulation as an optical response of the object, the improvement comprising: a laser source and an optical phase shifter and optical frequency modulator, which are provided for generating the intensity modulated beam, said elements providing means for effecting the intensity modulation of the laser beam in such a way that a modulation period of duration T=1/f 2 , where f 2 is a base frequency, comprises a time segment duration T 1 , in which the intensity is modulated with a periodic signal of carrier frequency f 1 , and a time segment duration T 2 , in which the intensity is constant; a semireflecting mirror being arranged in the intensity-modulated laser beam prior to interaction with the object for decoupling a beam to a regulating detector, and the regulating detector being connected with the electronic modulator group at the output side via a lock-in amplifier acting as a frequency-selective and phase-selective device, wherein the modulator group supplies a control signal to the phase shifter such that the phase displacement results in an intensity value for the elimination of an interfering component of the base frequency (f 2 ); and a measurement detector having an output which is coupled to a lock-in detector acting as a frequency-selective and phase-selective device, said detector beam being arranged in the beam path after interaction of the laser beam with the object, wherein the lock-in detector of the modulator group is adapted or tuned to the base frequency (f 2 ) which is generated as a result of photothermal modulation of the index of refraction by mixing the carrier frequency (f 1 ) and sideband frequencies (f 1 ±f 2 ) in the object.

Claim 34

The arrangement according to claim 29, wherein the phase shifter and frequency modulator are realized in integrated optics and a 3-dB expander is arranged for splitting and recombining the beam.