Multi-Photon Counting DSP for Raman Spectroscopy Sensitivity

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Solution Overview

Problem

Raman spectroscopy faces limitations in detecting low-Raman yield samples due to the low intensity of the Raman phenomenon, leading to missed photons in current single-threshold detection methods, which limits sensitivity and efficiency, especially for samples with intermediate Raman scattering.

Innovation Solution

A multi-photon counting approach using a high-speed data acquisition system and multi-threshold Digital Signal Processing (DSP) algorithm to differentiate photon arrival events by amplitude and time, enabling the detection of multiple photons and improving sensitivity and noise rejection.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of operation

If a single-threshold detection algorithm is used, then the detection simplicity is maintained, but photon detection accuracy deteriorates due to missed photons in multi-photon events

Engineering Contradiction:
Improvedetection simplicityVSAvoidphoton detection accuracy
Core Design Contradiction:
Ease of operationVSMeasurement precision

Solution Approach 1:

The single threshold is segmented into multiple thresholds (first threshold and second threshold) that operate at different sensitivity levels. The first threshold detects single photon events, while the second threshold detects multi-photon events, allowing the system to maintain simplicity while improving accuracy through structured threshold segmentation.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The detection algorithm transitions from a single-dimensional threshold comparison to a multi-dimensional evaluation by introducing time-resolved analysis and multiple threshold levels. This dimensional expansion enables the system to distinguish between single-photon and multi-photon events that would otherwise be indistinguishable with a single threshold.

Inventive Principle:
Principle #17Another dimension (Dimensionality change)

2Speed

If a single-threshold algorithm is used, then the processing speed is maintained, but sensitivity deteriorates for low-Raman yield samples

Engineering Contradiction:
Improveprocessing speedVSAvoidsensitivity
Core Design Contradiction:
SpeedVSReliability

Solution Approach 1:

The system performs preliminary threshold comparison to quickly eliminate obviously non-photon events, then applies more sophisticated multi-threshold analysis only to events that require it. This preliminary action maintains processing speed while improving sensitivity for low-Raman yield samples that produce weak signals.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The algorithm applies partial analysis (single-threshold processing) to most events to maintain speed, while applying excessive analysis (multi-threshold processing) only to events that exceed the first threshold, improving sensitivity without significantly impacting overall processing speed.

Inventive Principle:
Principle #16Partial or excessive action

3Quantity of substance

If a single-threshold detector is saturated, then the detection capability for strong scatterers is maintained, but the ability to observe changes in scatterer strength deteriorates

Engineering Contradiction:
Improvedetectable photon fluxVSAvoidscatterer strength observation
Core Design Contradiction:
Quantity of substanceVSMeasurement precision

Solution Approach 1:

The detection range is segmented into multiple dynamic ranges through different thresholds. The first threshold handles single-photon events, while the second threshold handles multi-photon events from strong scatterers. This segmentation prevents saturation by providing appropriate detection scales for different scatterer strengths.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The threshold settings are made dynamic rather than fixed, allowing the system to adapt to different scatterer strengths. The algorithm dynamically selects which threshold to apply based on the signal characteristics, maintaining the ability to observe changes in scatterer strength from weak to strong scatterers without saturation.

Inventive Principle:
Principle #15Dynamics

4Reliability

If multi-photon counting is implemented, then sensitivity is improved, but device complexity increases

Engineering Contradiction:
ImprovesensitivityVSAvoidprocessing algorithm complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The complex multi-photon detection task is segmented into simpler sub-tasks: first threshold comparison for single-photon events, and second threshold comparison for multi-photon events. This segmentation reduces the complexity of each individual comparison while achieving the overall sensitivity improvement.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

Different threshold strictness is applied locally to different signal regions. The first threshold provides lenient detection for weak signals, while the second threshold provides strict detection for strong signals. This local quality adjustment improves sensitivity without requiring uniformly complex processing throughout the entire detection range.

Inventive Principle:
Principle #3Local quality

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The multi-photon counting algorithm increases system sensitivity, extends the upper analysis limit for high Raman-yield compounds, and reduces experiment duration, as demonstrated by improved results in analyses of nitrate, isopropanol, and rhodamine 6G solutions, achieving 2.0 to 3.1-fold sensitivity gains compared to traditional single-threshold methods.

Implementation Method 1

a photomultiplier tube (PMT) response to each pulse of a pulsed laser

Methodology Applied
Scientific EffectPhotoelectric effect: Photoelectric Effect

Implementation Method 2

multi-threshold Digital Signal Processing (DSP) algorithm to differentiate photon arrival events by amplitude and time

Methodology Applied
Scientific EffectDigital signal processing:

Data Source

PatentUS20240093404A1Methods, algorithms and systems for sub-nanosecond digital signal processing of photomultiplier tube response to enable multi-photon counting in raman spectroscopy
Publication Date: 2024.03.21 NATIONAL TECHNOLOGY & ENGINEERING SOLUTIONS OF SANDIA LLC
  • US20240093404A1 patent drawing
  • US20240093404A1 patent drawing
  • US20240093404A1 patent drawing

AI summary

A computer-implemented method of determining the number of photons contributing to an output of a photonic sensor, including receiving an electrical signal from the photonic sensor proportional to a number of photons the photonic sensor detects at its input as a function of time, wherein the photonic sensor is calibrated such that a response of the photonic sensor to a single photon detected is in a waveform comprising an amplitude and time, wherein the product amplitude X time is statistically bounded, determining a probabilistic boundary between one or more of electrical, optical, and thermal sources of noise of the sensor, acquiring each response wave form from the sensor through analog-to-digital conversion with a resolution in amplitude and time corresponding to accuracy required in quantifying the response, storing each acquired response, individually, in real-time, or in buffered packets in digital form, determining the number of photons for a specific time resolved acquisition, and effecting a summation of the count of photon arrivals obtained based on amplitude evaluation from each specific time resolved acquisition, for all time resolved acquisitions performed in a given observation period, yielding the number of photon arrivals associated with the amplitude evaluation.